bluuebunny/crossref_metadata_2025 huggingface dataset:
Charge Polarization at a Au–TiC Interface and the Generation of Highly Active and Selective Catalysts for the Low‐Temperature Water–Gas Shift Reaction
Authors: Rodriguez José A. , Ramírez Pedro J. , Asara Gian Giacomo , Viñes Francesc , Evans Jaime , Liu Ping , Ricart Josep M. , Illas Francesc
Published: September 2014

Au atoms in contact with TiC(001) undergo significant charge polarization. Strong metal–support interactions make Au/TiC(001) an excellent catalyst for the low‐temperature water–gas shift (WGS), with turnover frequencies orders of magnitude larger than those observed for conventional metal/oxide catalysts. DFT calculations indicate that the WGS reaction follows an associative mechanism with HOCO as a key intermediate.
Green polyurethane from dimer acid based polyether polyols: Synthesis and characterization
Authors: Yu Feng , Saha Prosenjit , Suh Pyoung Won , Kim Jin Kuk
Published: September 2014

In this study, dimer acid (DA) obtained from waste soybean oil was used together with propylene oxide (PO) to obtain novel polyether polyols [prepolymers for polyurethanes (PUs)] through ring‐opening polymerization reaction. The average molecular weight of polyols was estimated by gel permeation chromatography and titration method. The substantial reaction between DA and PO was evident from FTIR and nuclear magnetic resonance spectroscopy. Subsequently, the polyols were reacted with chain extender [ethylene glycol, (EG)] and 4, 4 ‐ Diphenylmethane diisocyanate (MDI) to prepare green PUs. The effect of molar ratio variation of EG and MDI with a fixed amount of polyols was estimated by measuring hydrophobicity and mechanical strength of PUs. The molar ratio such as 1 : 4 : 5.7 of polyol : EG : MDI was found to exhibit maximum hydrophobicity and improved mechanical strength that were comparable with typical PU sample prepared from commercially available polyol, such as polypropylene glycol. FTIR spectroscopic analysis confirmed the chemical changes and possible crosslinking in PUs. Thermalgravimetric analysis and differential scanning calorimetry analysis also showed substantial thermal stability of the green PUs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41410.
Effects of the carboxyl‐ended hyperbranched polyester/platinum complex molecular weight on hydrosilylation activity and self‐assembled morphology
Authors: Xu Zhicai , Zhang Daohong , Li Junna , Chen Sufang , Li Tingcheng , Zhang Junheng , Zhang Aiqing , Chen Shenghui
Published: September 2014

Research on platinum catalysts with high activity and long life for hydrosilylation has attracted a great deal of interest because of the increasing price of platinum metal. In this study, we examined the effect of the molecular weight of carboxyl‐ended hyperbranched polyester/platinum complexes (HTD‐n–Pt's, where n = 1, 2, 3, or 4) on hydrosilylation activity and self‐assembled morphology. Relevant parameters tuning the morphology of self‐assemblies, such as the temperature, time, concentration, and relative humidity, were examined. All of the HTD‐n–Pt's with various molecular weights had much higher hydrosilylation activities than did the conventional homogeneous Speier's catalyst, and the HTD‐n–Pt could be self‐assembled into ordered two‐dimensional treelike structures with a fractal dimension ranging from 1.48 to 1.83; this indicated perfect fractal properties. With the increase of the HTD‐n–Pt molecular weight, the size of the self‐assembled treelike structures and the catalytic activity increased first and then decreased. The self‐assembly mechanism was speculated and analyzed by dynamic light scattering, X‐ray photoelectron spectroscopy, X‐ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy; these suggested good agreement with the diffusion‐limited aggregation theory of particles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41416.
A caution for conservation stocking as an approach for recovering Atlantic eels
Authors: Stacey Joshua A. , Pratt Thomas C. , Verreault Guy , Fox Michael G.
Published: September 2014

Worldwide concerns about declining eel stocks have resulted in the increased use of conservation stocking (i.e. the translocation of early eel life‐stages from areas of high recruitment to areas experiencing recruitment declines) as a recovery tool.

North Atlantic eels have complicated and incompletely understood life‐history strategies with major differences in life‐history parameters across the species’ broad distributions, and these differences may be important for migrating and spawning successfully.

Sex ratio, growth rate and size and age at maturation of American eels (Anguilla rostrata) stocked into the St. Lawrence River basin from donor areas over 2000 km away with differing life‐history characteristics were compared with those of naturally recruited eels to assess the effectiveness of a potential stocking programme in maintaining a sub‐population with unique life‐history characteristics (largest from across the species range, and exclusively female).

Stocked eels exhibited faster annual growth, had a different sex ratio, and matured and outmigrated at smaller sizes and ages than naturally recruited eels.

Conservation stocking should be applied with caution, as stocked eels appear to be following life‐history patterns comparable with conspecifics in the geographic range of the donor streams where they were collected. These findings cast doubt on the generally accepted hypothesis that the mechanisms driving eel life‐history variation are environmentally induced, and suggest that more care should be taken in assessing and matching the life‐history characteristics of donor and recipient sub‐populations if conservation stocking is expected to be an important recovery option for eel restoration.

© 2014 Her Majesty the Queen in Right of Canada. Aquatic Conservation: Marine and Freshwater Ecosystems © 2014 John Wiley & Sons, Ltd.
Mechanochromic Luminescence Characteristics of Pyridine‐Terminated Chromophores in the Solid State and in a Poly(vinyl alcohol) Matrix
Authors: Kondo Mizuho , Miura Seiya , Okumoto Kentaro , Hashimoto Mayuko , Kawatsuki Nobuhiro
Published: September 2014

Mechanoresponsive luminophores containing different substituted pyridine rings at the molecular terminus are synthesized and their photoluminescence properties are investigated. The solid chromophore with a 4‐substituted pyridine ring exhibits a reversible photoluminescent color change, while the 2‐substituted chromophore shows only a small change in luminescence, and the 3‐substituted chromophore displays an irreversible photoluminescent color change with mechanical grinding. A change of the sample color in response to mechanical grinding is also achieved for a dye‐dispersed poly(vinyl alcohol) film. Furthermore, a simultaneous acid and mechanoresponsive photoemission color change is achieved in the dye‐dispersed film.
Guaranteed Cost Consensus for Multi‐Agent Systems with Fixed Topologies
Authors: Wang Zhong , Xi Jianxiang , Yao Zhicheng , Liu Guangbin
Published: September 2014

Guaranteed cost consensus analysis and design problems for multi‐agent systems with fixed interaction topologies are investigated. Guaranteed cost consensus problems for multi‐agent systems are introduced to obtain a tradeoff between the consensus regulation performance and the energy consumption, where a cost function is constructed based on state errors among neighboring agents and control inputs of all agents. Sufficient conditions for guaranteed cost consensus and consensualization are given by the state space decomposition approach and the Lyapunov method, an upper bound of the cost function and the consensus value are determined respectively. It should be pointed out that these criteria of guaranteed cost consensus and consensualization are only related to the maximum eigenvalue of the Laplacian matrix associated with the interaction topology. A numerical simulation is given to show the effectiveness of the theoretical results.
Simultaneous efficient removal of high‐strength ammonia nitrogen and chemical oxygen demand from landfill leachate by using an extremely high ammonia nitrogen–resistant strain
Authors: Yu Dahai , Yang Jiyu , Fang Xuexun , Ren Hejun
Published: September 2014

Bioaugmentation is a promising technology for pollutant elimination from stressed environments, and it would provide an efficient way to solve challenges in traditional biotreatment of wastewater with high strength of ammonia nitrogen (NH4+‐N). A high NH4+‐N‐resistant bacteria strain, identified as Bacillus cereus (Jlu BC), was domesticated and isolated from the bacteria consortium in landfill leachate. Jlu BC could survive in 100 g/L NH4+‐N environment, which indicated its extremely high NH4+‐N tolerance than the stains found before. Jlu BC was employed in the bioaugmented system to remove high strength of NH4+‐N from landfill leachate, and to increase the removal efficiency, response surface methodology (RSM) was used for optimizing bioaugmentation degradation conditions. At the optimum condition (initial pH 7.33, 4.14 days, initial chemical oxygen demand [COD] concentration [18,000 mg/L], 3.5 mL inoculated domesticated bacteria strain, 0.3 mg/mL phosphorus supplement, 30 °C, and 170 rpm), 94.74 ± 3.8% removal rate of NH4+‐N was obtained, and the experiment data corresponded well with the predicted removal rate of the RSM models (95.50%). Furthermore, COD removal rate of 81.94 ± 1.4% was obtained simultaneously. The results presented are promising, and the screened strain would be of great practical importance in mature landfill leachate and other NH4+‐N enrichment wastewater pollution control.
Effects of recombinant IL‐17F intranasal inoculation against Streptococcus pneumoniae infection in a murine model
Authors: Chen Ling , Guo Sheng , Wu Liangxia , Hao Chunli , Xu Wanting , Zhang Jianhua
Published: September 2014

Interleukin‐17F (IL‐17F) is an important member of IL‐17 cytokine family, which plays important roles in host defense against microbial infections. Streptococcus pneumoniae is a common pathogen associated with several invasive and noninvasive pneumococcal diseases, and mucosal immune response plays crucial roles in defenses against pneumococcal infection. Thus, intranasal inoculation may be an alternative approach against pneumococci. In this study, BALB/c mice were intranasally inoculated with recombinant IL‐17F (rIL‐17F) prior to S. pneumoniae (American Type Culture Collection 6303, serotype 3) infection. As compared with the control group, numbers of total leukocyte, neutrophil, and macrophage in lungs were significantly increased in mice inoculated with rIL‐17F. The levels of macrophage inflammatory protein 1α (MIP‐1α), MIP‐2β, and interferon γ were significantly increased in bronchoalveolar lavage fluid and culture supernatant of splenocytes from mice inoculated with rIL‐17F. rIL‐17F inoculation also significantly elevated β‐defensin‐2 expression in lung tissues. Furthermore, compared with S. pneumoniae infection group, rIL‐17F inoculation prior to infection significantly reduced S. pneumoniae colonization in lungs. These findings demonstrated that rIL‐17F intranasal inoculation strengthened host defense against pneumococci, which may be developed to prevent pneumococcal infection.
Effect of acidic amino acids engineered into the active site cleft of Thermopolyspora flexuosa GH11 xylanase
Authors: Li He , Turunen Ossi
Published: September 2014

Thermopolyspora flexuosa GH11 xylanase (XYN11A) shows optimal activity at pH 6–7 and 75–80 °C. We studied how mutation to aspartic acid (N46D and V48D) in the vicinity of the catalytic acid/base affects the pH activity of highly thermophilic GH11 xylanase. Both mutations shifted the pH activity profile toward acidic pH. In general, the Km values were lower at pH 4–5 than at pH 6, and in line with this, the rate of hydrolysis of xylotetraose was slightly faster at pH 4 than at pH 6. The N46D mutation and also lower pH in XYN11A increased the hydrolysis of xylotriose. The Km value increased remarkably (from 2.5 to 11.6 mg/mL) because of V48D, which indicates the weakening of binding affinity of the substrate to the active site. Xylotetraose functioned well as a substrate for other enzymes, but with lowered reaction rate for V48D. Both N46D and V48D increased the enzyme inactivation by ionic liquid [emim]OAc. In conclusion, the pH activity profile could be shifted to acidic pH due to an effect from two different directions, but the tightly packed GH11 active site can cause steric problems for the mutations.
Periconceptional parental conditions and perimembranous ventricular septal defects in the offspring
Authors: Wijnands Kim P.J. , Zeilmaker Gerda A. , Meijer Willemijn M. , Helbing Willem A. , Steegers‐Theunissen Régine P.M.
Published: September 2014

Background: The perimembranous ventricular septal (pVSD) defect is the most common congenital heart disease phenotype. Several parental factors are associated with pVSD risk in the offspring. To contribute to the future prevention of pVSDs, we investigated associations with nongenetic parental conditions. Methods: In a case–control study with standardized data collection at 17 months after birth, 115 parents of a child with pVSD and 484 parents of a healthy child completed questionnaires about periconceptional nongenetic conditions. Univariable and multivariable logistic regression analyses were used to estimate odds ratios (OR) with 95% confidence intervals (95% CI). Results: Complete data were available for 588 families (98%). Maternal risk conditions associated with pVSD offspring were a positive family history of congenital heart disease (OR, 2.61; 95%CI, 0.98–6.91), medication use (OR, 1.80; 95%CI, 1.13–2.85) and advanced age (OR, 1.07; 95%CI, 1.02–1.12). Exposure to phthalates (OR, 1.93; 95%CI, 1.05–3.54) was the only paternal risk condition associated with pVSD offspring. Conclusion: Four periconceptional parental conditions contributed to pVSD risk in the offspring. Couples planning pregnancy should be counseled on these risk conditions which are partially modifiable to contribute to the future prevention of pVSDs. Birth Defects Research (Part A) 100:944–950, 2014. © 2014 Wiley Periodicals, Inc.
Developmental outcomes in young children born to mothers with west nile illness during pregnancy
Authors: Sirois Patricia A. , Pridjian Gabriella , McRae Scott , Hinckley Alison F. , Rasmussen Sonja A. , Kissinger Patricia , Buekens Pierre , Hayes Edward B. , O'Leary Daniel R. , Swan Kenneth F. , Xiong Xu , Wesson Dawn M.
Published: September 2014

Background

West Nile virus (WNV) infection is associated with acute morbidity and mortality in adults and children. Information on the effects of maternal WNV illness during pregnancy on early childhood development is limited. This study was designed to examine the relationship between maternal WNV illness during pregnancy and birth and developmental outcomes at age 3 years.

Methods

Mother‐child participants were identified using a national surveillance registry for women with WNV illness during pregnancy. Maternal and infant health data and relevant family characteristics were obtained through medical record reviews and maternal questionnaires. All infants received ophthalmologic examinations. Child development was evaluated at age 3 years using the Bayley Scales of Infant and Toddler Development–Third Edition (Bayley‐III).

Results

As a group, the children's (N = 11) birth weight, head circumference, and infant ophthalmologic examination results were within age expectations; one child was born preterm (gestational age 36 weeks). Mean (SD) age at the time of Bayley‐III testing was 36.7 (3.8) months. The group's mean performance on the Bayley‐III was at or above age level in all domains, but one child showed a mild delay in the Adaptive domain. The variability observed in this sample (1/53 [1.9%] Domain scores < −2.0 SDs) was consistent with expectations based upon the distribution of Bayley‐III Domain scores in the general population.

Conclusion

Maternal WNV infection does not appear to be associated with global developmental delays in young children. These results are preliminary, however, and require confirmation in future research. Birth Defects Research (Part A) 100:792–796, 2014. © 2014 Wiley Periodicals, Inc.
Analysis of renal anomalies in VACTERL association
Authors: Cunningham Bridget K. , Khromykh Alina , Martinez Ariel F. , Carney Tyler , Hadley Donald W. , Solomon Benjamin D.
Published: September 2014

Background

VACTERL association refers to a combination of congenital anomalies that can include: vertebral anomalies, anal atresia, cardiac malformations, tracheo‐esophageal fistula with esophageal atresia, renal anomalies (typically structural renal anomalies), and limb anomalies.

Methods

We conducted a description of a case series to characterize renal findings in a cohort of patients with VACTERL association. Out of the overall cohort, 48 patients (with at least three component features of VACTERL and who had abdominal ultrasound performed) met criteria for analysis. Four other patients were additionally analyzed separately, with the hypothesis that subtle renal system anomalies may occur in patients who would not otherwise meet criteria for VACTERL association.

Results

Thirty‐three (69%) of the 48 patients had a clinical manifestation affecting the renal system. The most common renal manifestation (RM) was vesicoureteral reflux (VUR) in addition to a structural defect (present in 27%), followed by unilateral renal agenesis (24%), and then dysplastic/multicystic kidneys or duplicated collected system (18% for each). Twenty‐two (88%) of the 25 patients with a structural RM had an associated anorectal malformation. Individuals with either isolated lower anatomic anomalies, or both upper and lower anatomic anomalies were not statistically more likely to have a structural renal defect than those with isolated upper anatomic anomalies (p = 0.22, p = 0.284, respectively).

Conclusion

Given the high prevalence of isolated VUR in our cohort, we recommend a screening VCUG or other imaging modality be obtained to evaluate for VUR if initial renal ultrasound shows evidence of obstruction or renal scarring, as well as ongoing evaluation of renal health. Birth Defects Research (Part A) 100:801–805, 2014. © 2014 Wiley Periodicals, Inc.
Intermediate frequency magnetic field generated by a wireless power transmission device does not cause genotoxicity in vitro
Authors: Shi Dejing , Zhu Chunbo , Lu Rengui , Mao Shitong , Qi Yanhua
Published: September 2014

The aim of this study was to evaluate effects of intermediate frequency magnetic fields (IFMF) generated by a wireless power transmission (WPT) based on magnetic resonance from the perspective of cellular genotoxicity on cultured human lens epithelial cells (HLECs). We evaluated the effects of exposure to 90 kHz magnetic fields at 93.36 µT on cellular genotoxicity in vitro for 2 and 4 h. The magnetic flux density is approximately 3.5 times higher than the reference level recommended by the International Commission on Non‐Ionizing Radiation Protection (ICNIRP) guidelines. For assessment of genotoxicity, we studied cellular proliferation, apoptosis and DNA damage by Cell Counting Kit‐8 (CCK‐8) assay, flow cytometry analysis, alkaline comet assay and phosphorylated histone H2AX (γH2AX) foci formation test. We did not detect any effect of a 90 kHz IFMF generated by WPT based on magnetic resonance on cell proliferation, apoptosis, comet assay, and γH2AX foci formation test. Our results indicated that exposure to 90 kHz IFMF generated by WPT based on magnetic resonance at 93.36 µT for 2 and 4 h does not cause detectable cellular genotoxicity. Bioelectromagnetics. 35:512–518, 2014. © 2014 Wiley Periodicals, Inc.
Chromatographic and electrophoretic strategies for the chiral separation and quantification of d‐ and l‐threo methylphenidate in biological matrices
Authors: Allen Serena A. , Pond Brooks B.
Published: September 2014

Commercially available methylphenidate (MPH) exists as a racemic mixture composed of the d‐ and l‐threo enantiomers. Various pharmacokinetic studies of MPH have shown a greater pharmacological potency of the d‐threo enantiomer. Furthermore, it was deduced that the stereoselective cleavage of MPH to produce ritalinic acid (RA) by human carboxylesterase results in a higher oral bioavailability of the d‐threo enantiomer. As a requirement for pharmaceutical regulation authorities, efforts have been made to determine the differential biological distribution of d‐ and l‐threo MPH and RA enantiomers. In support of these efforts, numerous analytical procedures have been developed for the chiral separation and quantification of MPH enantiomers in a variety of biological matrices. The available methodologies accomplish the enantioseparation and quantification of MPH using gas chromatography, liquid chromatography or capillary electrophoretic techniques coupled with a variety of detectors. The current review discusses the technical procedures involved, and the sensitivity and selectivity of these assays. Copyright © 2014 John Wiley & Sons, Ltd.
Position‐based rigid‐body dynamics
Authors: Deul Crispin , Charrier Patrick , Bender Jan
Published: September 2014

We propose a position‐based approach for large‐scale simulations of rigid bodies at interactive frame rates. Our method solves positional constraints between rigid bodies and can therefore be seamlessly integrated into other position‐based methods. Interaction of particles and rigid bodies through common constraints enables two‐way coupling with deformables. The method exhibits exceptional performance and stability while being user controllable and easy to implement. Various results demonstrate the practicability of our method for the resolution of collisions, contacts, stacking and joint constraints. Copyright © 2014 John Wiley & Sons, Ltd.
Combining inverse blending and Jacobian‐based inverse kinematics to improve accuracy in human motion generation
Authors: Zhang Liang , Brunnett Guido
Published: September 2014

We present in the paper a hybrid method for motion editing combining motion blending and Jacobian‐based inverse kinematics (IK). When the original constraints are changed, a blending‐based IK solver is first employed to find an adequate joint configuration coarsely. Using linear motion blending, this search corresponds to a gradient‐based minimization in the weight space. The found solution is then improved by a Jacobian‐based IK solver by further minimizing the distance between the end effectors and constraints. To accelerate the searching in the weight space, we introduce a weight map, which pre‐computes the good starting positions for the gradient‐based minimization. The advantages of our approach are threefold: first, more realistic motions can be generated by utilizing motion blending techniques, compared with pure Jacobian‐based IK. The blended results also increase the rate of convergence of the Jacobian‐based IK solver. Second, the Jacobian‐based IK solver modifies poses in the pose configuration space and the computational cost does not scale with the number of examples. Third, it is possible to extrapolate the given example motions with a Jacobian‐based IK solver, while it is generally difficult with pure blending‐based techniques. Copyright © 2014 John Wiley & Sons, Ltd.
Reiter's syndrome and hearing loss: a possible association?
Authors: Monsanto Rafael C. , Neto Arlindo C. L. , Lorenzetti Fábio T. M.
Published: September 2014

Key clinical message

Patient complained of hearing loss and tinnitus after the onset of Reiter's syndrome. Audiometry confirmed the hearing loss on the left ear; blood work showed increased erythrocyte sedimentation rate and C3 fraction of the complement. Genotyping for HLA‐B27 was positive. Treatment with prednisolone did not improve the hearing levels.
Tandem Gold Self‐Relay Catalysis for the Synthesis of 2,3‐Dihydropyridin‐4(1 H)‐ones: Combination of σ and π Lewis Acid Properties of Gold Salts
Authors: Fustero Santos , Miró Javier , Sánchez‐Roselló María , del Pozo Carlos
Published: September 2014

The dual ability of gold salts to act as π‐ and σ Lewis acids has been exploited in a tandem self‐relay catalysis. Thus, triphenylphosphanegold(I) triflate mediated the intramolecular carbonyl addition of the amide functionality of homoprogargyl amides to a triple bond. The formation of a σ complex of the gold salt with the intermediate oxazine promoted a nucleophilic addition followed by a Petasis–Ferrier rearrangement. This tandem protocol, catalyzed by the same gold salt under the same reaction conditions, gave rise to the efficient synthesis of 2,3‐dihydropyridin‐4‐(1 H)‐ones, which contain a cyclic quaternary α‐amino acid unit. The asymmetric version was performed by generating the starting materials from the corresponding sulfinylimines.
Pseudorotational Landscape of Seven‐Membered Rings: The Most Stable Chair and Twist‐Boat Conformers of ε‐Caprolactone
Authors: Jahn Michaela K. , Dewald David A. , Vallejo‐López Montserrat , Cocinero Emilio J. , Lesarri Alberto , Zou Wenli , Cremer Dieter , Grabow Jens‐Uwe
Published: September 2014

The conformational landscape and ring‐puckering properties of ε‐caprolactone have been analyzed by using microwave spectroscopy and quantum chemical calculations. Two conformers were detected in a supersonic jet expansion, the most stable form being a chair containing the ester group in its rectangular flap. This conformation benefits from reduced CH2 bond eclipsing and angle strain, while π‐electron delocalization in the ester group is increased. The derived effective structure of the chair form satisfactorily agrees with the calculated near‐equilibrium structure. A twist‐boat conformer was also identified (9.4 kJ mol−1 higher in energy at CCSD(T)/aug‐cc‐pVTZ level), and was located in the boat‐twist‐boat pseudorotation cycle of the seven‐membered ring. Three other low‐energy conformers were investigated and characterized in terms of the four puckering coordinates of the seven‐membered ring. Potential interconversions in the four‐dimensional conformation space are also discussed.
Characterisation of Alkane σ‐Complexes
Authors: Young Rowan D.
Published: September 2014

Alkane σ‐complexes have evolved from a curious phenomenon to an intermediate of intense interest, fuelling research into the area. Over the last fifteen years, metal alkane complex characterisation has evolved to incorporate reports employing UV/Vis, IR and NMR spectroscopy, and X‐ray and neutron diffractometry. Previously, due to the sparse geometric characterisation of alkane σ‐complexes, assumptions regarding bonding geometries and selectivities were made by comparison to related σ‐complexes, or by analysis of CH activation products. This minireview assembles relevant literature that illuminates the metrics of alkane–metal bonding, and critically analyses the binding mode, selectivity and stability of alkane complexes.
Mechanism of Alkyne Alkoxycarbonylation at a Pd Catalyst with P,N Hemilabile Ligands: A Density Functional Study
Authors: Crawford L. Ellis , Cole‐Hamilton David J. , Drent Eite , Bühl Michael
Published: September 2014

A detailed mechanism for alkyne alkoxycarbonylation mediated by a palladium catalyst has been characterised at the B3PW91‐D3/PCM level of density functional theory (including bulk solvation and dispersion corrections). This transformation, investigated via the methoxycarbonylation of propyne, involves a uniquely dual role for the P,N hemilabile ligand acting co‐catalytically as both an in situ base and proton relay coupled with a Pd0 centre, allowing for surmountable barriers (highest ΔG≠ of 22.9 kcal mol−1 for alcoholysis). This proton‐shuffle between methanol and coordinated propyne accounts for experimental requirements (high acid concentration) and reproduces observed regioselectivities as a function of ligand structure. A simple ligand modification is proposed, which is predicted to improve catalytic turnover by three orders of magnitude.
Cube‐in‐Cube Hollow Cu9S5 Nanostructures with Enhanced Photocatalytic Activities in Solar H2 Evolution
Authors: Xu Miao , Wang Min , Ye Tiannan , Liang Na , Jin Lun , Zai Jiantao , Qian Xuefeng
Published: September 2014

Invited for the cover of this issue is the group of Xuefeng Qian at Shanghai Jiao Tong University. The image depicts hydrogen being produced from water by solar energy. Read the full text of the article at 10.1002/chem.201403683.
Comparison of methods for estimation of the covariance matrix of measurement errors
Authors: Feital Thiago , Prata Diego Martinez , Pinto José Carlos
Published: September 2014

Measurement errors normally present in measured process variables can mask the actual process conditions and lead to wrong operational decisions. This is due not only to the imprecise measured values but also to the propagation of the measurement error through process models used to perform control and optimization tasks. One possible alternative to deal with this problem is to characterize the measurement errors online and to incorporate the obtained information in the process operation. The present work analyzes the performances of different methods used for characterization of measurement errors in different scenarios commonly found in the industrial practice. Based on the obtained results, a method is proposed for direct evaluation of measurement errors at plant site.
Identification of Green Tea Catechins as Potent Inhibitors of the Polo‐Box Domain of Polo‐Like kinase 1
Authors: Shan Hong‐Mei , Shi Yanxia , Quan Junmin
Published: September 2014

Polo‐like kinase 1 (PLK1) plays crucial functions in multiple stages of mitosis and is considered to be a potential drug target for cancer therapy. The functions of PLK1 are mediated by its N‐terminal kinase domain and C‐terminal polo‐box domain (PBD). Most inhibitors targeting the kinase domain of PLK1 have a selectivity issue because of a high degree of structural conservation within kinase domains of all protein kinases. Here, we combined virtual and experimental screenings to identify green tea catechins as potent inhibitors of the PLK1 PBD. Initially, (−)‐epigallocatechin, one of the main components of green tea polyphenols, was found to significantly block the binding of fluorescein‐labeled phosphopeptide to the PBD at a concentration of 10 μm. Next, additional catechins were evaluated for their dose‐dependent inhibition of the PBD and preliminary structure–activity relationships were derived. Cellular analysis further showed that catechins interfere with the proper subcellular localization of PLK1, lead to cell‐cycle arrest in the S and G2M phases, and induce growth inhibition of several human cancer cell types, such as breast adenocarcinoma (MCF7), lung adenocarcinoma (A549), and cervical adenocarcinoma (HeLa). Our data provides new insight into understanding the anticancer activities of green tea catechins.
Childhood Maltreatment, Shame‐Proneness and Self‐Criticism in Social Anxiety Disorder: A Sequential Mediational Model
Authors: Shahar Ben , Doron Guy , Szepsenwol Ohad
Published: September 2014

Previous research has shown a robust link between emotional abuse and neglect with social anxiety symptoms. However, the mechanisms through which these links operate are less clear. We hypothesized a model in which early experiences of abuse and neglect create aversive shame states, internalized into a stable shame‐based cognitive–affective schema. Self‐criticism is conceptualized as a safety strategy designed to conceal flaws and prevent further experiences of shame. However, self‐criticism maintains negative self‐perceptions and insecurity in social situations. To provide preliminary, cross‐sectional support for this model, a nonclinical community sample of 219 adults from Israel (110 females, mean age = 38.7) completed measures of childhood trauma, shame‐proneness, self‐criticism and social anxiety symptoms. A sequential mediational model showed that emotional abuse, but not emotional neglect, predicted shame‐proneness, which in turn predicted self‐criticism, which in turn predicted social anxiety symptoms. These results provide initial evidence supporting the role of shame and self‐criticism in the development and maintenance of social anxiety disorder. The clinical implications of these findings are discussed Copyright © 2014 John Wiley & Sons, Ltd.

Key Practitioner Message

Previous research has shown that histories of emotional abuse and emotional neglect predict social anxiety symptoms, but the mechanisms that underlie these associations are not clear.

Using psycho‐evolutionary and emotion‐focused perspectives, the findings of the current study suggest that shame and self‐criticism play an important role in social anxiety and may mediate the link between emotional abuse and symptoms.

These findings also suggest that therapeutic interventions specifically targeting shame and self‐criticism should be incorporated into treatments for social anxiety, especially with socially anxious patients with abuse histories.
Novel Pathways to 2,5‐Dimethylfuran via Biomass‐Derived 5‐(Chloromethyl)furfural
Authors: Dutta Saikat , Mascal Mark
Published: September 2014

2,5‐Dimethylfuran (DMF) is one of the most actively pursued biomass‐derived chemicals due to the fact that it can serve both as a biofuel and an intermediate for drop‐in terephthalate polymers. DMF can be accessed via catalytic hydrogenation of 5‐(hydroxymethyl)furfural (HMF), but the difficult accessibility of HMF from cellulosic biomass is a major impediment to the commercial development of such a process. Alternatively, 5‐(chloromethyl)furfural (CMF) is freely accessible in high yield directly from raw biomass and is shown here to be efficiently reduced to DMF under mild conditions via simple derivatives (aldimine, acetal).
Early adverse experience increases emotional reactivity in juvenile rhesus macaques: Relation to amygdala volume
Authors: Howell Brittany R. , Grand Alison P. , McCormack Kai M. , Shi Yundi , LaPrarie Jamie L. , Maestripieri Dario , Styner Martin A. , Sanchez Mar M.
Published: September 2014

This study investigated the impact of infant maltreatment on juvenile rhesus monkeys' behavioral reactivity to novel stimuli and its associations with amygdala volume. Behavioral reactivity to novel stimuli of varying threat intensity was measured using Approach/Avoidance (AA) and Human Intruder (HI) tasks. In vivo magnetic resonance imaging (MRI) was used to measure amygdala volume. Interestingly, group behavioral differences were context‐dependent. When exposed to a human intruder, maltreated subjects displayed more anxious behaviors than controls; however, when presented with fear‐evoking objects, maltreated animals exhibited increased aggression and a shorter latency to inspect the objects. Finally, under testing conditions with the lowest levels of threat (neutral novel objects) maltreated animals also showed shorter latencies to inspect objects, and reduced avoidance and increased exploration compared to controls. This suggests alterations in threat assessment and less behavioral inhibition in animals with early adverse experience compared to controls. Some of these behavioral responses were associated with amygdala volume, which was positively correlated with abuse rates received during infancy, particularly reflecting a relationship with exploration, consistent with previous studies. © 2014 Wiley Periodicals, Inc. Dev Psychobiol 56: 1735–1746, 2014.
The prevalence and adverse associations of stigmatization in people with eating disorders
Authors: Griffiths Scott , Mond Jonathan M. , Murray Stuart B. , Touyz Stephen
Published: September 2014

Objective

To date, studies of stigma relating to eating disorders have been largely confined to surveys of the public. We sought to examine the prevalence and correlates of stigma as reported by individuals with eating disorders.

Method

An online survey designed to assess frequency of exposure to potentially stigmatizing attitudes and beliefs as well as the perceived impact of this on health and well‐being was completed by a cross‐national sample of 317 individuals with anorexia nervosa (n = 165), bulimia nervosa (n = 66), or Eating Disorder Not Otherwise Specified (EDNOS; n = 86).

Results

Participants rated two beliefs as both particularly common and particularly damaging, namely “I should be able to just pull myself together” and “I am personally responsible for my condition”. Participants with bulimia nervosa more commonly experienced the belief that they had “no self‐control” and male participants more commonly experienced the belief that they were “less of a man”. More frequent stigmatization was associated with higher levels of eating disorder psychopathology, a longer duration of disorder, lower self‐esteem, and more self‐stigma of seeking psychological help.

Discussion

Stigma towards individuals with eating disorders, as experienced by sufferers, is common and associated with numerous adverse outcomes. The perceptions that eating disorders are trivial and self‐inflicted should be a focus of destigmatization interventions. Efforts to reduce stigma towards individuals with bulimia nervosa may need to focus on perceptions of self‐control, whereas efforts to reduce stigma towards males with eating disorders may need to focus on perceptions of masculinity/manhood. © 2014 Wiley Periodicals, Inc. (Int J Eat Disord 2015; 48:767–774)
Individual phenotypic variation reduces interaction strengths in a consumer–resource system
Authors: Gibert Jean P. , Brassil Chad E.
Published: September 2014

Natural populations often show variation in traits that can affect the strength of interspecific interactions. Interaction strengths in turn influence the fate of pairwise interacting populations and the stability of food webs. Understanding the mechanisms relating individual phenotypic variation to interaction strengths is thus central to assess how trait variation affects population and community dynamics. We incorporated nonheritable variation in attack rates and handling times into a classical consumer–resource model to investigate how variation may alter interaction strengths, population dynamics, species persistence, and invasiveness. We found that individual variation influences species persistence through its effect on interaction strengths. In many scenarios, interaction strengths decrease with variation, which in turn affects species coexistence and stability. Because environmental change alters the direction and strength of selection acting upon phenotypic traits, our results have implications for species coexistence in a context of habitat fragmentation, climate change, and the arrival of exotic species to native ecosystems.
Facile Synthesis of 9,10,19,20‐Tetraarylporphycenes
Authors: Ganapathi Emandi , Chatterjee Tamal , Ravikanth Mangalampalli
Published: September 2014

A simple route was developed for the synthesis of 9,10,19,20‐tetraarylporphycenes by combining both McMurry and oxidative synthetic strategies and using readily available precursors. The desired 5,6‐diaryldipyrroethenes, which were prepared in multigram quantities over two steps, were used to prepare 9,10,19,20‐tetraarylporphycenes under mild acid‐catalyzed conditions. As 5,6‐diaryldipyrroethene precursors can easily be prepared in multigram quantities, this method is useful for the preparation of meso‐tetrarylporphycenes that contain different aryl substituents. The molecular structures of these macrocycles were determined by HRMS analysis as well as 1D and 2D NMR studies. The tetraarylporphycenes exhibited a strong Soret band at approximately 380 nm and three Q bands in the region of 580–655 nm. The tetraarylprophycenes are reasonably fluorescent and stable under redox conditions.
Palladium‐Catalyzed Oxidative Synthesis of Aromatic Ketones Using Olefins as Acyl Equivalents through Selective ortho Aromatic C–H Bond Activation
Authors: Khemnar Ashok B. , Bhanage Bhalchandra M.
Published: September 2014

An efficient catalytic system has been developed for selective ortho‐acylation of arenes by oxidative C–H bond activation using a palladium catalyst. Olefins were oxidized to the corresponding aldehydes/benzoyl radicals, which, on coupling with 2‐phenylpyridine, gave the corresponding acylated products in good to excellent yields. 1‐Phenylpyrazole also reacts with substituted olefins to give the acylation products in good yields.
Grain‐size distribution in open channel flow by mixing length approach
Authors: Pal D. , Ghoshal K.
Published: September 2014

A mathematical model is developed by theoretical analysis for predicting the grain‐size distribution in suspension over sand and sand‐gravel beds. By including the viscous shear stress of sediment–fluid mixture and the Reynolds shear stress in terms of mixing length of sediment‐mixed fluid, a system of integrodifferential equations of velocity and suspension concentration is developed. The effect of hindered settling is considered in the settling velocity of sediment particle and the effect of particle–particle interaction is taken into account in the reference level. Apart from this, incipient motion probability, pick‐up probability and nonceasing probability of a sediment particle are included in the reference concentration. The proposed system of integrodifferential equations is converted into a system of first‐order differential equations, and the fourth‐order Runge–Kutta method has been adopted for solving the system of equations. The numerical solution of the proposed system reflects the behavior of fluid velocity and grain‐size distribution with changing vertical height over a sediment bed comprising nonuniform grain sizes. The computed values of velocity and grain‐size distribution are compared with a limited data set due to the unavailability of sufficient data in literature, and good agreement has been observed between them. The proposed model provides least errors in comparison to the other existing models in literature. Copyright © 2014 John Wiley & Sons, Ltd.
Anti‐inflammatory effects of a casein hydrolysate and its peptide‐enriched fractions on TNFα‐challenged Caco‐2 cells and LPS‐challenged porcine colonic explants
Authors: Mukhopadhya Anindya , Noronha Nessa , Bahar Bojlul , Ryan Marion T. , Murray Brian A. , Kelly Phil M. , O'Loughlin Ian B. , O'Doherty John V. , Sweeney Torres
Published: September 2014

Bioactive milk peptides are reported to illicit a range of physiological benefits and have been proposed as potential functional food ingredients. The objective of this study was to characterize the anti‐inflammatory properties of sodium caseinate (NaCAS), its enzyme hydrolysate (EH) and peptide‐enriched fractions (5 kDa retentate [R], 1 kDaR and 1 kDa permeate [P]), both in vitro using a Caco‐2 cell line, and also ex vivo using a porcine colonic tissue explant system. Caco‐2 cells were stimulated with tumour necrosis factor alpha (TNFα) and co‐treated with casein hydrolysates for 24 h. Following this, interleukin (IL)‐8 concentrations in the supernatant were measured using enzyme‐linked immunosorbent assay. Porcine colonic tissue was stimulated with lipopolysaccharide and co‐treated with casein hydrolysates for 3 h. The expression of a panel of inflammatory cytokines was measured using qPCR. While dexamethasone reduced the IL‐8 concentration by 41.6%, the 1 kDaR and 1 kDaP fractions reduced IL‐8 by 68.7% and 66.1%, respectively, relative to TNFα‐stimulated Caco‐2 cells (P < 0.05). In the ex vivo system, only the 1 kDaR fraction elicited a decrease in IL1‐α, IL1‐β, IL‐8, TGF‐β and IL‐10 expression (P < 0.05). This study provides evidence that the bioactive peptides present in the 1 kDaR fraction of the NaCAS hydrolysate possess anti‐inflammatory properties in vitro and ex vivo. Further in vivo analysis of the anti‐inflammatory properties of the 1 kDaR is proposed.
Numerical modeling of saturated soils, based on Smoothed Particle Hydrodynamics (SPH)
Authors: Grabe Jürgen , Stefanova Bozhana
Published: September 2014

Smoothed particle hydrodynamics (SPH) is a mesh‐free numerical method originally developed in the 1970s for astrophysical analysis. In the recent decades, it has been applied to a wide range of research fields, including fluid and solid mechanics, hydrodynamics and coastal and geotechnical engineering. This paper presents an application of SPH to the problem of interaction between the soil skeleton and the pore water in saturated soils. The formulation of the equations of conservation in SPH has been modified so that a drag force due to seepage is introduced and calculated using Darcy's law. Two test cases are considered for the analysis: a basic drainage of a vertical sand column due to gravity and seepage through a vertical dam (also known as the Muskat problem). Both simulations show very good agreement with the analytical solutions. The results prove the potential of SPH.

Numerische Modellierung gesättigter Böden mit der Smoothed Particle Hydrodynamics – Teil 1: Grundwasserströmungsanalyse. Die Smoothed Particle Hydrodynamics (SPH) ist eine netzfreie numerische Methode, die ursprünglich in den 1970er‐Jahren für astrophysikalische Berechnungen entwickelt wurde. In den vergangenen Jahrzehnten hat sie zahlreiche Anwendungsgebiete gefunden, u. a. Fluid‐ und Strukturmechanik, Hydrodynamik, Küsteningenieurwesen und auch Geotechnik. Dieser Artikel zeigt eine Anwendung der SPH zur Untersuchung der Interaktion zwischen Korngerüst und Porenwasser wassergesättigter Böden. Zu diesem Zweck wurde die Formulierung der Erhaltungsgleichungen um eine Strömungskraft basierend auf dem Gesetz von Darcy erweitert. Zur Validierung werden zwei Sickerströmungsprobleme betrachtet: die Entwässerung einer Bodensäule unter Gravitation und die Strömung durch einen vertikalen Damm, auch bekannt als das Muskat‐Problem. Beide Simulationen haben eine sehr gute Übereinstimmung mit den analytischen Lösungen gezeigt. Die Ergebnisse bestätigen das Potential der SPH.
Kritische Anmerkungen zu DIN 18321 – ATV Düsenstrahlarbeiten
Authors: Schulze Bertram , Jud Holger
Published: September 2014

Die Allgemeinen Technischen Vertragsbedingungen für Bauleistungen, die Bestandteil der VOB Teil C sind, sollen die Zusammenarbeit von Auftraggeber und Auftragnehmer regeln und erleichtern. Insbesondere im Falle von Unstimmigkeiten bei Abrechnungsfragen sollen die ATV Hilfestellungen für gerichtliche und außergerichtliche Einigungen liefern. Sie sollen somit dem Rechtsfrieden dienen. Nach Auffassung der Verfasser ist dies mit den ATV Düsenstrahlarbeiten, DIN 18321, aber nicht der Fall. In einer angeregten Überarbeitung sollte dem verfahrensbedingt engen Zusammenwirken von Boden‐ und Baustoff/Verfahren durch eine klare Zuweisung von Auftraggeber‐ und Auftragnehmeraufgaben und durch eine gemeinsam zu verantwortende Qualitätssicherung stärker Rechnung getragen werden als bisher. Der zuständige Normenausschuss hat eine detaillierte Zusammenstellung der Verbesserungsvorschläge erhalten.

Critical notes on DIN 18321 – ATV Jet Grouting Works. The purpose of the General Technical Terms of Contract for Building Works (ATV), which are included in part C of the Contract Rules for Award of Public Works Contracts (VOB), is to regulate and facilitate the cooperation between client and contractor. Especially in the case of discrepancies on billing issues, the ATV is meant to provide support for arrangements both in and out of court. The general purpose is to give legal certainty. In the authors' view, the ATV Jet Grouting Works, DIN 18321:2012‐09, do not achieve this purpose. In a suggested revision, the close interaction of soil and building material/treatment needs to be taken more into account, by a clearly defined allocation of client and contractor tasks as well as by a shared responsibility with respect to quality assurance. The responsible standards committee has been sent a detailed compilation of the suggestions for improvement.