bluuebunny/crossref_metadata_2025 huggingface dataset:
Asymmetric Hydrogenation of Maleic Acid Diesters and Anhydrides
Authors: Bernasconi Maurizio , Müller Marc‐André , Pfaltz Andreas
Published: April 2014

Asymmetric hydrogenation of maleic and fumaric acid derivatives with iridium catalysts based on N,P ligands provides an efficient route to chiral enantioenriched succinates. A new catalyst derived from a 2,6‐difluorophenyl‐substituted pyridine‐phosphinite ligand was developed and enables the conversion of a wide range of 2‐alkyl and 2‐arylmaleic acid diesters into the corresponding succinates in high enantiomeric purity. Mixtures of cis/trans substrates can be hydrogenated in an enantioconvergent fashion with high enantioselectivity, and further enhances the scope of this transformation. The products are valuable chiral building blocks with a structural motif found in many bioactive compounds, such as metalloproteinase inhibitors.
Boron Radical Cations from the Facile Oxidation of Electron‐Rich Diborenes
Authors: Bissinger Philipp , Braunschweig Holger , Damme Alexander , Kupfer Thomas , Krummenacher Ivo , Vargas Alfredo
Published: April 2014

The realization of a phosphine‐stabilized diborene, Et3P⋅(Mes)BB(Mes)⋅PEt3 (4), by KC8 reduction of Et3P⋅B2Mes2Br2 in benzene enabled the evaluation and comparison of its electronic structure to the previously described NHC‐stabilized diborene IMe⋅(Dur)BB(Dur)⋅IMe (1). Importantly, both species feature unusual electron‐rich boron centers. However, cyclic voltammetry, UV/Vis spectroscopy, and DFT calculations revealed a significant influence of the Lewis base on the reduction potential and absorption behavior of the BB double bond system. Thus, the stronger σ‐donor strength and larger electronegativity of the NHC ligand results in an energetically higher‐lying HOMO, making 1 a stronger neutral reductant as 4 (1: E1/2=−1.55 V; 4: −1.05 V), and a smaller HOMO–LUMO gap of 1 accompanied by a noticeable red‐shift of its lowest‐energy absorption band with respect to 4. Owing to the highly negative reduction potentials, 1 and 4 were easily oxidized to afford rare boron‐centered radical cations (5 and 6).
A review of fracturing fluid systems used for hydraulic fracturing of oil and gas wells
Authors: Barati Reza , Liang Jenn‐Tai
Published: April 2014

Hydraulic fracturing has been used by the oil and gas industry as a way to boost hydrocarbon production since 1947. Recent advances in fracturing technologies, such as multistage fracturing in horizontal wells, are responsible for the latest hydrocarbon production boom in the US. Linear or crosslinked guars are the most commonly used fluids in traditional fracturing operations. The main functions of these fluids are to open/propagate the fractures and transport proppants into the fractures. Proppants are usually applied to form a thin layer between fracture faces to prop the fractures open at the end of the fracturing process. Chemical breakers are used to break the polymers at the end of the fracturing process so as to provide highly conductive fractures. Concerns over fracture conductivity damage by viscous fluids in ultra‐tight formations found in unconventional reservoirs prompted the industry to develop an alternative fracturing fluid called “slickwater”. It consists mainly of water with a very low concentration of linear polymer. The low concentration polymer serves primarily to reduce the friction loss along the flow lines. Proppant‐carrying capability of this type of fluids is still a subject of debate among industry experts. Constraints on local water availability and the potential for damage to formations have led the industry to develop other types of fracturing fluids such as viscoelastic surfactants and energized fluids. This article reviews both the traditional viscous fluids used in conventional hydraulic fracturing operations as well as the new family of fluids being developed for both traditional and unconventional reservoirs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40735.
Influence of the processing parameters and composition on the thermal stability of PLA/nanoclay bio‐nanocomposites
Authors: Iturrondobeitia Maider , Okariz Ana , Guraya Teresa , Zaldua Ane‐Miren , Ibarretxe Julen
Published: April 2014

Poly(lactic acid) (PLA) is one the most promising bio‐based and biodegradable polymer. However, its low thermal stability limits the range of applications and complicates its transformation via the most industrial common processes. The novelty of this work is studying the thermal stability of PLA and PLA/clay nanocomposites during use, as a function of the composition and using a wide range of extrusion and injection moulding processing parameters. To improve the thermal stability of the PLA, laminar silicates containing different organomodifications have been added (Cloisite 20A and Cloisite 30B). The results show that the processing conditions and composition define the morphology of the bio‐nanocomposites, which plays key role in defining final thermal properties of the material. In general, clays improve the thermal stability of the processed material, increasing the degradation temperature and decreasing the degradation rate under a wide range of processing conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40747.
Quasi‐Min‐Max Model Predictive Control for Image‐Based Visual Servoing with Tensor Product Model Transformation
Authors: Wang T. T. , Xie W. F. , Liu G. D. , Zhao Y. M.
Published: April 2014

This paper presents a novel image‐based visual servoing (IBVS) controller based on quasi‐min‐max model predictive control (MPC). By transforming the image Jacobian matrix (i.e. interaction matrix) into a convex combination of linear time‐invariant vertices form with the tensor‐product (TP) model transformation method, the visual servoing system is represented as a polytopic linear parameter‐varying (LPV) system. A robust controller is designed for the robotic visual servoing system subject to input and output constraints such as robot physical limitations and visibility constraints. The control signal is calculated online by carrying out the convex optimization involving linear matrix inequalities (LMIs) in model predictive control. The proposed visual servoing method avoids the inverse of the image Jacobian matrix and hence can solve the intractable problems for the classical IBVS controller, such as large displacements between the initial and the desired position of the camera. The ability of handling constraints can keep the image features in the boundary of the desired field of view (FOV). To verify the effectiveness of the proposed algorithm, the simulation results on a 6 degrees‐of‐freedom (DOF) robot manipulator with eye‐in‐hand configuration are presented and discussed.
From chemical platform molecules to new biosolvents: Design engineering as a substitution methodology
Authors: Bergez‐Lacoste Manon , Thiebaud‐Roux Sophie , De Caro Pascale , Fabre Jean‐François , Gerbaud Vincent , Mouloungui Zéphirin
Published: April 2014

The substitution of conventional solvents, in line with regulation changes, requires the use of appropriate methodologies able to generate candidate molecules. Starting from the widely used trial and error approach, we developed two improved, time‐ and cost‐saving methodologies, involving the prediction of molecule properties and reverse design. Reverse design is an innovative methodology to design biosolvents through a virtual laboratory: stages of generation of molecular structures and properties prediction are integrated into a computer‐aided molecular design tool providing solutions that meet targeted specifications. These two substitution methodologies were applied in a case study aiming at replacing acetone and methyl ethyl ketone for the solubilization of epoxy resin prepolymers. The generation of performing biosolvents was carried out from furfural as a bio‐based platform molecule, thanks to the prediction of different relevant properties (physico‐chemical, safety, and environmental characteristics). The reverse design succeeded in ranking these solvent candidates according to their capacity to match the required specifications.
Continuous antibody purification using precipitation: An important step forward
Authors: Velayudhan Ajoy
Published: April 2014

Recent advances in cell culture have reduced upstream costs, and made downstream processing the more expensive component of biologics manufacturing. Within downstream processing, the chromatographic steps have usually been the most expensive, on the one hand because chromatographic steps are traditionally run in batch mode and on the other because resins are typically more expensive per unit mass of product than other bioproduct‐contact materials [1, 2]. There have been many attempts to consider alternatives to chromatography [3, 4], but the comparatively high resolution of chromatography, combined with the bioprocess industry's wealth of experience in using the various chromatographic modes, have made it hard to replace in a manufacturing setting. In this issue of Biotechnology Journal Hammerschmid et al. [5] make several original contributions to this discussion.
Seasonal Changes of Flavonoid Content in Melittis melissophyllum L. (Lamiaceae)
Authors: Skrzypczak‐Pietraszek Ewa , Pietraszek Jacek
Published: April 2014

Melittis melissophyllum L., a medicinal plant currently used in the folk medicine, was analyzed for the content of flavonoid compounds. The plants were collected in two locations in Poland in May and September. MeOH Extracts from the leaves and flowers (separately) were analyzed by HPLC‐DAD. Eight compounds were identified in all the samples and quantitatively analyzed as cinaroside (=luteolin 7‐O‐glucoside), rutin, myricetin, quercitrin, quercetin, luteolin, kaempferol, and apigenin. M. melissophyllum accumulated the highest total amounts of flavonoids in May (flowers: from 258 to 271 mg/100 g dry weight (dw); leaves: from 143 to 155 mg/100 g dw) and significantly lower ones in September (leaves: from 83 to 92 mg/100 g dw). The main compound was cinaroside (May: up to 249 mg/100 g dw; September: up to 43 mg/100 g dw). Advanced multivariate statistical techniques (cluster analysis (CA) and principal component analysis (PCA)) were used to characterize the sample populations and to analyze the data. We report, for the first time, the results of the quantitative analysis of M. melissophyllum flavonoids and seasonal changes in their accumulation. Our results show that the time of harvesting has a significant influence on the flavonoid content in M. melissophyllum, while the geographical location does not have such an effect.
Further Antibacterial Geranium macrorrhizum L. Metabolites and Synthesis of Epoxygermacrones
Authors: Radulović Niko S. , Zlatković Dragan , Dekić Milan , Stojanović‐Radić Zorica
Published: April 2014

4,5‐ and 1,10‐Epoxygermacrones were isolated from the essential oil of aerial parts of Geranium macrorrhizum L. (Geraniaceae). The structures of the epoxy derivatives were deduced from their 1D‐ and 2D‐NMR spectra, molecular modeling, and confirmed by synthesis starting from germacrone. The epoxy compounds were screened for their antimicrobial activities by a microdilution assay, which revealed high activities of both compounds against Bacillus subtilis (minimum inhibitory concentrations (M/Cs) determined were 4.3 and 43 nmol/ml for 1,10‐ and 4,5‐epoxygermacrone, resp.) and Pseudomonas aeruginosa (0.043 and 0.855 μmol/ml for 1,10‐ and 4,5‐epoxygermacrone, resp.). The discovery and observed activity of the two epoxides fills the gap in our knowledge of the active principles in this highly renowned ethnomedicinal plant species.
Limonoids from Azadirachta indica var. siamensis Extracts and Their Cytotoxic and Melanogenesis‐Inhibitory Activities
Authors: Manosroi Aranya , Kitdamrongtham Worapong , Ishii Kenta , Shinozaki Takuro , Tachi Yosuke , Takagi Mio , Ebina Kodai , Zhang Jie , Manosroi Jiradej , Akihisa Rima , Akihisa Toshihiro
Published: April 2014

Six new limonoids, 7‐benzoyl‐17‐epinimbocinol (5), 3‐acetyl‐7‐tigloylnimbidinin (8), 1‐isovaleroyl‐1‐detigloylsalanninolide (15), 2,3‐dihydro‐3α‐methoxynimbolide (16), deacetyl‐20,21‐epoxy‐20,22‐dihydro‐21‐deoxyisonimbinolide (26), and deacetyl‐20,21,22,23‐tetrahydro‐20,22‐dihydroxy‐21,23‐dimethoxynimbin (27), along with 28 known limonoids, 1–4, 6, 7, 9–14, 17–25, and 28–34, and two known flavonoids, 35 and 36, have been isolated from the extracts of bark, leaves, roots, and seeds of Azadirachta indica A. Juss. var. siamensis Valeton (Siamese neem tree; Meliaceae). The structures of the new compounds were elucidated on the basis of extensive spectroscopic analysis and comparison with literature data. All of these compounds were evaluated for their cytotoxic activities against leukemia (HL60), lung (A549), stomach (AZ521), and breast (SK‐BR‐3) cancer cell lines. Eleven compounds, 1, 2, 4–7, 13, 16, 17, 29, and 30, exhibited potent cytotoxicities against one or more cell lines with IC50 values in the range of 0.1–9.3 μM. Compound 16 induced apoptotic cell death in AZ521 cells upon evaluation of the apoptosis‐inducing activity by flow cytometric analysis. Western blot analysis on AZ521 cells revealed that compound 16 activated caspases‐3, ‐8, and ‐9, while increasing the ratio of Bax/Bcl‐2. This suggested that 16 induced apoptosis via both mitochondrial and death receptor pathways in AZ521. In addition, upon evaluation of all compounds against the melanogenesis in B16 melanoma cells induced with α‐melanocyte‐stimulating hormone (α‐MSH), 20 limonoids, i.e., 1–3, 6, 9–11, 18, 19, 21–29, 32, and 34, and two flavonoids, 35 and 36, exhibited melanogenesis‐inhibitory activities, with no, or almost no, toxicities to the cells at lower and/or higher concentrations, which were more potent than the reference arbutin, a known melanogenesis inhibitor. Western blot analysis showed that nimbin (18) reduced the protein levels of microphtalmia‐associated transcription factor (MITF), tyrosinase, tyrosine‐related protein 1 (TRP‐1), and TRP‐2 mostly in a concentration‐dependent manner, indicating that 18 inhibits melanogenesis on a α‐MSH‐stimulated B16 melanoma cells by, at least in part, inhibiting the expression of MITF, followed by decreasing the expression of tyrosinase, TRP‐1, and TRP‐2.
Air‐Core Size Measurement of Operating Hydrocyclone by Electrical Resistance Tomography
Authors: Rakesh Arugonda , Kumar Reddy Vakamalla T. S. R , Narasimha Mangadoddy
Published: April 2014

Electrical resistance tomography (ERT) allows to measure hydrocyclone internal flow dynamics in situ. A dual‐plane high‐speed ERT system is proposed to map two‐phase distributions with varying operational parameters. Experimental results are presented in terms of air‐core diameter and its size variation for various feed flow rates and design variables. The total variation algorithm provides the best results compared to Tikhonov and Gauss‐Newton algorithms. The influence of finite element method mesh size on air‐core resolution is evaluated. High‐speed video imaging and a volume‐of‐fluid‐based two‐phase computational fluid dynamics (CFD) model are adopted to determine the air‐core size. Cross validation of air‐core size and shape is performed by ERT measurements with CFD simulations and high‐speed video imaging.
Ultrafine Grinding of Limestone with Sodium Polyacrylates as Additives in Ordinary Portland Cement Mortar
Authors: Ohenoja Katja , Breitung‐Faes Sandra , Kinnunen Päivö , Illikainen Mirja , Saari Juha , Kwade Arno , Niinimäki Jouko
Published: April 2014

Sodium polyacrylates permit a higher solids concentration during grinding, reducing the resulting particle size and/or specific energy consumption. Their impact on fine and ultrafine grinding of limestone was studied. Sodium polyacrylate with a low polydispersity index was found to be the most effective grinding aid for limestone and consequently applied for further nano‐grinding experiments. Nano‐grinding was most energy‐efficient with the smallest grinding medium size. These ground nano‐sized CaCO3 particles with sodium polyacrylate on the surface accelerated the hydration of ordinary Portland cement cement paste.
Performance Enhancement of Bulk Heterojunction Solar Cells with Direct Growth of CdS‐Cluster‐Decorated Graphene Nanosheets
Authors: Yuan Kai , Chen Lie , Tan Licheng , Chen Yiwang
Published: April 2014

Two‐dimensional graphene–CdS (G–CdS) semiconductor hybrid nanosheets were synthesized in situ by graphene oxide (GO) quantum wells and a metal–xanthate precursor through a one‐step growth process. Incorporation of G–CdS nanosheets into a photoactive film consisting of poly[4,8‐bis‐(2‐ethyl‐hexyl‐thiophene‐5‐yl)‐benzo[1,2‐b:4,5‐b]dithiophene‐2,6‐diyl]‐alt‐[2‐(2‐ethyl‐hexanoyl)‐thieno[3,4‐b]thiophen‐4,6‐diyl] (PBDTTT‐C‐T) and [6,6]‐phenyl C70 butyric acid methyl ester (PC70BM) effectively decreases the exciton lifetime to accelerate exciton dissociation. More importantly, the decreasing energy levels of PBDTTT‐C‐T, PC70BM, and G–CdS produces versatile heterojunction interfaces of PBDTTT‐C‐T:PC70BM, PBDTTT‐C‐T:G–CdS, and PBDTTT‐C‐T:PC70BM:G–CdS; this offers multi‐charge‐transfer channels for more efficient charge separation and transfer. The charge transfer in the blend film also depends on the G–CdS nanosheet loadings. In addition, G–CdS nanosheets improve light utilization and charge mobility in the photoactive layer. As a result, by incorporation of G–CdS nanosheets into the active layer, the power‐conversion efficiency of inverted solar cells based on PBDTTT‐C‐T and PC71BM is improved from 6.0 % for a reference device without G–CdS nanosheets to 7.5 % for the device with 1.5wt % G–CdS nanosheets, due to the dramatically enhanced short‐circuit current. Combined with the advantageous mechanical properties of the PBDTTT‐C‐T:PC70BM:G–CdS active layer, the novel CdS‐cluster‐decorated graphene hybrid nanomaterials provide a promising approach to improve the device performance.
Chiral Framework with 20‐Ring Channels Exhibiting Metal‐Activator‐Free Photoluminescence
Authors: Huang Hui‐Lin , Luo Zih‐Jie , Kuo Yu‐Chih , Wang Sue‐Lein
Published: April 2014

The use of biomass‐derived sucrose has unprecedentedly induced the first chiral zinc phosphite structure with 20R channels along with a series of acentric frameworks, unveiling a facile synthesis of chiral nanoporous frameworks. The 20R‐channel structures are metal‐activator free but display blue‐to‐white photoluminescence under long UV excitation.
Efficient Engineering and Production Concepts for Products in Regulated Environments – Dream or Nightmare?
Authors: Strube Jochen , Ditz Reinhard , Fröhlich Holger , Köster Dirk , Grützner Thomas , Koch Jörg , Schütte Rüdiger
Published: April 2014

Manufacturing of chemical‐pharmaceutical products is moving increasingly fast on a global scale. Therefore, developing and starting up production facilities fast, with high quality, and at reasonable costs has become extremely challenging. Engineering concepts like modularization, standardization and simultaneous/parallel engineering are discussed as methods for speeding up process design and filing for regulatory approval. Transfer from batch to continuous operation mode of production is pointed out as the key‐issue in such strategies.
Process and Product Development of Electrodes for Lithium‐Ion Cells
Authors: Kaiser Jörg , Wenzel Valentin , Nirschl Hermann , Bitsch Boris , Willenbacher Norbert , Baunach Michael , Schmitt Marcel , Jaiser Stefan , Scharfer Philip , Schabel Wilhelm
Published: April 2014

Die Elektromobilität und die Speicherung regenerativ erzeugter elektrischer Energie stellen hohe Anforderungen an die Leistung und Kosten von Li‐Ionen‐Zellen. Sie erfordern ein tiefgreifendes Verständnis über die Materialeigenschaften der Rohstoffe und die verfahrenstechnischen Prozesse zur Herstellung der Elektroden. Zahlreiche Parameter müssen in der Produktentwicklung und späteren Produktion gemessen und gesteuert werden, um gezielt spezifische Zelleigenschaften einzustellen und gleichzeitig das Verständnis für einen stabilen Fertigungsprozess zu etablieren.
Implementation of Organic Solvent Nanofiltration in Specialty Chemicals Production: Potential and Challenges
Authors: Zeidler Stefanie , Kätzel Uwe , Schmalz Dirk
Published: April 2014

Die organophile Nanofiltration (OSN) ist ein vielversprechendes Werkzeug für die Prozessintensivierung. Bei der Produktion von Spezialchemikalien in einem Mehrproduktanlagen‐Umfeld werden besondere Anforderungen an Membranen und Anlagendesign gestellt, die hier näher erläutert werden. Das Fehlen von Erfahrungswissen und detaillierten Stofftransportmodellen erschwert die Prozessentwicklung der OSN. Aus systematischen Untersuchungen mit verschiedenen Membranen und Lösungsmitteln werden Regeln entwickelt, die die schnelle Identifizierung der geeignetsten Membran für ein gegebenes Stoffsystem ermöglichen.
Decomposition of 2‐Mercaptoethyl O‐Ester: SN2 Displacement or Acyl Transfer? A Theoretical Study
Authors: Zhang Shenshen , Qi Chenze , Wang Chen
Published: April 2014

The mechanism for the decomposition of 2‐mercaptoethyl O‐ester was theoretically investigated. The mechanism that 2‐mercaptoethyl O‐ester undergoes an SN2 displacement of the O atom by the S atom on α‐C is much favored over the mechanism of N‐to‐S acyl transfer. The length of the alcohol moiety has large effects on the decomposition efficiency of thiol‐substituted alkyl O‐esters. The reactivities of these esters are controlled by distortion energies. Only 2‐mercaptoethyl O‐ester can undergo the decomposition at room temperature due to the low distortion energy to achieve the transition state geometry. If the thiol group of 2‐mercaptoethyl O‐ester is replaced by an amino group, the N‐to‐N acyl transfer mechanism is more favored than the SN2 displacement mechanism.
Manganese(III) Salen Complex Immobilized on Fe3O4 Magnetic Nanoparticles: The Efficient, Green and Reusable Nanocatalyst
Authors: Sadeghzadeh Seyed Mohsen , Daneshfar Faeze , Malekzadeh Maryam
Published: April 2014

A new Fe3O4 magnetic nanoparticles supported manganese salen complex was successfully prepared by attaching manganese acetates to a novel N,N′‐bis(salicylidine)ethylenediamine ligand functionalized Fe3O4. The as‐prepared catalyst was characterized by TGA, XRD, FTIR, VSM, and TEM. It was found to be an efficient catalyst for the synthesis of benzopyranopyrimidines in aqueous medium. High catalytic activity and ease of recovery from the reaction mixture using external magnet, and several reuse times without significant losses in performance are additional eco‐friendly attributes of this catalytic system.
Guideline‐concordant cancer care and survival among American Indian/Alaskan Native patients
Authors: Javid Sara H. , Varghese Thomas K. , Morris Arden M. , Porter Michael P. , He Hao , Buchwald Dedra , Flum David R. ,   for the Collaborative to Improve Native Cancer Outcomes (CINCO)
Published: April 2014

BACKGROUND

American Indians/Alaskan Natives (AI/ANs) have the worst 5‐year cancer survival of all racial/ethnic groups in the United States. Causes for this disparity are unknown. The authors of this report examined the receipt of cancer treatment among AI/AN patients compared with white patients.

METHODS

This was a retrospective cohort study of 338,204 patients who were diagnosed at age ≥65 years with breast, colon, lung, or prostate cancer between 1996 and 2005 in the Surveillance, Epidemiology, and End Results‐Medicare database. Nationally accepted guidelines for surgical and adjuvant therapy and surveillance were selected as metrics of optimal, guideline‐concordant care. Treatment analyses compared AI/ANs with matched whites.

RESULTS

Across cancer types, AI/ANs were less likely to receive optimal cancer treatment and were less likely to undergo surgery (P ≤ .025 for all cancers). Adjuvant therapy rates were significantly lower for AI/AN patients with breast cancer (P < .001) and colon cancer (P = .001). Rates of post‐treatment surveillance also were lower among AI/ANs and were statistically significantly lower for AI/AN patients with breast cancer (P = .002) and prostate cancer (P < .001). Nonreceipt of optimal cancer treatment was associated with significantly worse survival across cancer types. Disease‐specific survival for those who did not undergo surgery was significantly lower for patients with breast cancer (hazard ratio [HR], 0.62), colon cancer (HR, 0.74), prostate cancer (HR, 0.52), and lung cancer (HR, 0.36). Survival rates also were significantly lower for those patients who did not receive adjuvant therapy for breast cancer (HR, 0.56), colon cancer (HR, 0.59), or prostate cancer (HR, 0.81; all 95% confidence intervals were <1.0).

CONCLUSIONS

Fewer AI/AN patients than white patients received guideline‐concordant cancer treatment across the 4 most common cancers. Efforts to explain these differences are critical to improving cancer care and survival for AI/AN patients. Cancer 2014;120:2183–2190. © 2014 American Cancer Society.
Critical Sets of Elliptic Equations
Authors: Cheeger Jeff , Naber Aaron , Valtorta Daniele
Published: April 2014

Given a solution u to a linear, homogeneous, second‐order elliptic equation with Lipschitz coefficients, we introduce techniques for giving improved estimates of the critical set 𝒷(u)u {x :|δu|(x) = 0}, as well as the first estimates on the effective critical set 𝒷r(u), which roughly consists of points x such that the gradient of u is small somewhere on Br(x) compared to the nonconstancy of u. The results are new even for harmonic functions on ℝn. Given such a u, the standard first‐order stratification {lk} of u separates points x based on the degrees of symmetry of the leading‐order polynomial of u‐u(x). In this paper we give a quantitative stratification of u, which separates points based on the number of almost symmetries of approximate leading‐order polynomials of u at various scales. We prove effective estimates on the volume of the tubular neighborhood of each , which lead directly to (n‐2 + ɛ)‐Minkowski type estimates for the critical set of u. With some additional regularity assumptions on the coefficients of the equation, we refine the estimate to give new proofs of the uniform (n‐2)‐Hausdorff measure estimate on the critical set and singular sets of u.© 2014 Wiley Periodicals, Inc.
Making campus bridging work for researchers: Can campus bridging experts accelerate discovery?
Authors: Michael Scott , Thota Abhinav , Henschel Robert , Knepper Rich
Published: April 2014

The computational demands of an ever increasing number of scholars at universities and research institutions throughout the country are outgrowing the capacity of desktop workstations. Researchers are turning to high performance computing facilities, both on their campuses and at regional and national centers, to run simulations and analyze data. The Extreme Science and Engineering Discovery Environment (XSEDE) is one of the first places researchers turn to when they outgrow their campus resources. XSEDE machines are far larger (by at least an order of magnitude) than what most universities offer. Transitioning from a campus resource to an XSEDE resource is seldom a trivial task. XSEDE has taken many steps to make this transition easier, including the campus bridging initiative, the Campus Champions program, and the Extended Collaborative Support Service program. In this paper, we present a new facet to the campus bridging initiative in the form of the campus bridging expert, an information technology professional dedicated to aid researchers in transitioning from desktop, to campus, to regional, and to national resources. We outline the current state of affairs and explore how campus bridging experts could provide maximal impact for minimal investment on the part of the organizing body. Copyright © 2014 John Wiley & Sons, Ltd.
The Impact of Corporate Social Responsibility on Customer Satisfaction, Relationship Maintenance and Loyalty in the Shipping Industry
Authors: Shin Youngran , Thai Vinh V.
Published: April 2014

This paper aims to examine the impact of perceived corporate social responsibility (CSR), with a focus on ethical and environment questions related to the constructs of customer satisfaction (CS), relationship maintenance (RM) and customer loyalty (CL), on determining the attitudinal and behavioural loyalty and maintenance of customers in the shipping industry. For this purpose, this study enhances its empirical validity by collecting data from 214 respondents in South Korea and testing the hypothesis using structure equation modelling. It was found that (1) CSR is an effective relationship marketing tool that requires further research to investigate its benefits; (2) systemic investigation in CSR activities in the shipping industry finds publishing CSR reports the most preferred tool among major shipping companies; and (3) there is a strong empirical evidence which supports that values have a significant impact on the customers' perception of CSR performance. Copyright © 2014 John Wiley & Sons, Ltd and ERP Environment
Investigation of phantom circuit benefits for next generation xDSL systems
Authors: Lafata Pavel
Published: April 2014

This paper is focused on measurements and analysis of phantom mode benefits in G.fast and next generation xDSL systems. The investigation is based on real measurements performed for a multi‐quad metallic cable together with theoretical evaluations of phantom circuit potentials. Because the presence of phantom circuits leads into increasing the summary crosstalk level in a metallic cable, the application of a phantom mode is questionable in practice. That is why the investigation was performed, and conclusions provided in this paper can be helpful to decide potential benefits of this method for future applications. The elimination of a crosstalk can be performed by using advanced modulation techniques such as vectored discrete multi‐tone modulation (VDMT); however, its application in practice is limited because of its complexity and computational demands. That is why several scenarios are currently being discussed with either no VDMT application or with only partial crosstalk compensation. Because of that, this paper is focused on comparing the results for a first scenario without using any far‐end crosstalk (FEXT) elimination technique, whereas a second scenario is based on partial FEXT suppression by VDMT application, to decide the effectiveness of using phantom modes in practice. Copyright © 2014 John Wiley & Sons, Ltd.
Rütteltisch‐Versuche an Gebäuden aus wärmedämmendem Ziegelmauerwerk
Authors: Jäger Andreas , Mendes Luis , Degée Hervé , Mordant Christophe , Lu Suikai
Published: April 2014

Im Rahmen des Europäischen Forschungsprojekts SERIES (Seismic Engineering Research Infrastructures for European Synergies) wurden unter der Leitung von Wienerberger und in Zusammenarbeit mit einem internationalen Forscherteam Rütteltischversuche an Mauerwerksgebäuden aus mit Dämmstoff gefüllten Ziegeln durchgeführt.

Das Verhalten von dämmstoffgefüllten Ziegeln unter seismischer Belastung wurde bis jetzt nur durch zyklische Schubversuche an einzelnen Wänden untersucht. Deshalb war das Ziel dieser Untersuchungen, das seismische Verhalten von unbewehrtem Mauerwerk aus diesen Ziegeln an realen Gebäuden im Maßstab 1:1 zu evaluieren. Es wurden zwei Gebäude mit unterschiedlicher Grundrissgeometrie errichtet und mit dem 3D‐Rütteltisch unterschiedlichen seismischen Belastungsstufen mit steigender Intensität ausgesetzt.

In diesem Beitrag werden die wichtigsten experimentellen Ergebnisse zum Tragverhalten der Gebäude zusammengefasst. Der experimentelle Aufbau wird detailliert dargestellt und das dynamische Verhalten und die beobachteten Versagensmechanismen werden diskutiert. Aus den Versuchsergebnissen werden Verhaltensbeiwerte abgeleitet und Zwischenstockwerksverschiebungen in Abhängigkeit der seismischen Intensität ausgewertet. Der Artikel schließt mit einer Zusammenfassung und den daraus abgeleiteten wichtigsten Schlussfolgerungen.

Shaking table tests on constructions built of thermal insulating clay block masonry. In the scope of the European research project SERIES (Seismic Engineering Research Infrastructures for European Synergies), shaking table tests on masonry constructions built with insulation filled clay blocks have been conducted under the lead of Wienerberger in cooperation with an international research team.

The behavior of insulation filled blocks under seismic action has been tested so far only via cyclic shear tests on single walls. The goal of these investigations was to assess the seismic behavior of unreinforced masonry built with such clay blocks on real scale buildings. For this purpose, two full‐scale mock‐ups with different geometries were erected and tested on the 3D shaking table using a series of seismic records with increasing intensity.

In this paper, the most relevant experimental results of the load bearing behavior of the mock‐ups are summarized. The experimental setup is presented in detail and the dynamic behavior and the observed failure modes are discussed. Behavior factors are evaluated from the experimental results and interstory drift values are computed in relation to the seismic intensity. The paper closes with a summary and the most important conclusions.
Zur Planung, Ausführung und Leistungsfähigkeit des Außenwand‐Decken‐Knotens von monolithischem Ziegelmauerwerk
Authors: Kranzler Thomas
Published: April 2014

Mit zunehmenden Wärmeschutzanforderungen gehen stets auch erhöhte Anforderungen an die Außenwände von Gebäuden einher. Bei monolithischen Außenwänden, also Außenwänden aus hochwärmedämmenden Mauerziegeln, die keine Zusatzdämmung z. B. in Form von Wärmedämmverbundsystemen (WDVS) benötigen, ist eine sorgfältige Planung und Ausführung des Details “Außenwand‐Decken‐Knoten“ daher von immer größerer Bedeutung. Neben den Aspekten des Wärme‐ und Feuchteschutzes muss dieses Detail gleichzeitig auch den Anforderungen resultierend aus Statik, Brand‐ und Schallschutz genügen. Da die separate Berücksichtigung der einzelnen Teilaspekte mitunter jedoch zu diametral entgegen stehenden Ausführungsvarianten des Details “Außenwand‐Decken‐Knoten“ führen würde, gilt es, eine Ausführungsvariante zu finden, die alle an das Detail gestellten Anforderungen bestmöglich erfüllt. Im folgenden Beitrag wird ein Vorschlag für die “ideale“ Ausführung des Details “Außenwand‐Decken‐Knoten“ unter Berücksichtigung der bauphysikalischen, statischen und konstruktiven Belange vorgestellt.

Design, construction and performance of the wall‐slab‐junction of monolithic external masonry walls made with thermal‐insulating clay blocks. Monolithic external walls are external walls made with high‐insulating clay blocks which do not require an additional external thermal insulation composite system (ETICS). For the planning, the design and the execution of these walls, the respective wall‐slab‐junction is of particular interest, because single aspects of building physics and the requirements in terms of design would lead to diametrically opposing variants of the detail “wall‐slab‐junction”. In this paper, a proposal for an optimized execution of this detail will be submitted, taking into account all relevant aspects. Its performance will be presented.
Ausführung und bauphysikalische Belange von zweischaligen Haustrennwänden
Authors: Gierga Michael , Schneiderhan Tobias
Published: April 2014

Die Ausführung zweischaliger Haustrennwände ist seit vielen Jahren Stand der Technik. Dennoch können bei Mauerwerkswänden immer wieder Mängel festgestellt werden, welche die Schalldämmung, den Wärme‐ und Feuchteschutz und deren Gebrauchstauglichkeit einschränken. Dabei ist eine solide Ausführung auf Basis einfacher Planungsregeln ohne weiteres möglich. Dieser Beitrag stellt die erforderlichen Maßnahmen im Zusammenhang mit den unterschiedlichen bauphysikalischen Anforderungsdisziplinen dar und hilft Mängel zu vermeiden.

Design and building physics issues of double partition walls. The execution of double partition walls has long been state of the art. However, defects can be detected in masonry walls over and over again that restrict the sound reduction, heat and humidity protection and their usability. Here, a solid design based on simple planning rules is readily possible. This article presents the necessary measures in connection with the different building physics requirement disciplines and helps to avoid defects.
Effect of eplerenone in percutaneous coronary intervention‐treated post‐myocardial infarction patients with left ventricular systolic dysfunction: a subanalysis of theEPHESUStrial
Authors: Iqbal Javaid , Fay Renaud , Adlam David , Squire Iain , Parviz Yasir , Gunn Julian , Pitt Bertram , Zannad Faiez
Published: April 2014

Aims

EPHESUSwas a multicentre, double‐blind clinical trial in which 6632 patients with acute myocardial infarction (AMI) complicated byLVsystolic dysfunction (LVSD) were randomized to receive eplerenone (n= 3319) or placebo (n= 3313). A total of 1580EPHESUSpatients were treated withPCI, which is now the standard treatment forAMI. ThisEPHESUSsubstudy examined the effects of eplerenone upon cardiovascular outcomes inPCI‐treated patients.

Methods and results

EPHESUSpatients were divided intoPCI‐treated and non‐PCI‐treated cohorts, and the effect of eplerenone upon mortality and other major adverse cardiovascular outcomes was assessed in each cohort. ThePCI‐treated patients (n= 1580) were younger, and had better renal function and fewer co‐morbidities than non‐PCI‐treated patients (n= 5052). Cardiovascular mortality was significantly lower inPCI‐treated patients as compared with non‐PCI‐treated patients (7% vs. 16%,P< 0.0001). However, the incidence of non‐fatal events was similar inPCI‐treated and non‐PCI‐treated cohorts. There was no statistical difference between thePCI‐treated and non‐PCI‐treated cohorts in the primary or secondary outcomes of the trial. Eplerenone administration, compared with placebo, in thePCI‐treated cohort did not affectPCI‐related clinical outcomes, including recurrence of angina, the occurrence of acute coronary syndromes, or the need for further revascularization.

Conclusions

The beneficial effects of eplerenone in theEPHESUStrial exist for bothPCI‐ and non‐PCI‐treatedAMIpatients withLVSD. Eplerenone has minimal, if any, effect upon reducingPCI‐related adverse events in thePCI‐treated cohort.
Attachment of Chelating Ligand Pockets to Tinorganyl Moieties
Authors: Barth Beatrix E. K. , Harms Klaus , Dehnen Stefanie
Published: April 2014

Several approaches have been undertaken to realize the synthesis of a new tinorganyl compound with a 2,2′,6′,2″‐terpyridine moiety. A synthesis pathway consisting of five steps with an overall yield of 51 % was successful in producing Ph3Sn(CH2)3OPhttpy [HOttpy = 2,6‐bis(2′‐pyridyl)‐4′‐(p‐hydroxyphenyl)pyridine], and insight has been gained into (partial) halogenation reactions with this unprecedented tinorganyl compound. Halogenation with hydroiodic acid produced a new dinuclear complex cation that resulted from head‐to‐tail coordination of two monocations. Furthermore, synthesis and yields of already known intermediates have been optimized. The products were analyzed and identified by 119Sn NMR, 1H NMR, and 13C NMR spectroscopy and ESI mass spectrometry, as well as by means of single‐crystal X‐ray diffraction.
The Synthesis, Structures and Polymorphism of the Dimeric Trivalent Rare‐Earth 3,5‐Dimethylpyrazolate Complexes [Ln(Me2pz)3(thf)]2
Authors: Deacon Glen B. , Harika Rita , Junk Peter C. , Skelton Brian W. , Werner Daniel , White Allan H.
Published: April 2014

A variety of rare‐earth 3,5‐dimethylpyrazolate (Me2pz) complexes have been synthesised by (i) the direct reaction of Hg‐activated metal with Me2pzH as a pro‐ligand at elevated temperatures, (ii) by redox transmetalation/protolysis with the lanthanoid element, Hg(C6F5)2, and Me2pzH, and (iii) by protolysis of tris[bis(trimethylsilyl)amido]cerium(III) with Me2pzH. Each product, upon crystallisation from tetrahydrofuran (thf), formed a dimeric complex, [Ln(Me2pz)3(thf)]2 (Ln = La, Ce, Pr, Nd, Ho, Yb, or Lu). Despite the common formulation, two completely different structures were observed in two distinct crystallographic “domains of existence”, together presumptively spanning the gamut of Ln and Y. For the larger rare‐earth ions (La–Pr), there are two terminal η2‐Me2pz ligands and one thf donor on each Ln atom, with the metal atoms being linked by a pair of bridging pyrazolate ligands of an uncommon type (η2:η5), resulting in formal ten‐coordination. A Me2pzH complex [Ce(Me2pz)3(Me2pzH)], although not isomorphous, has a similar structure. For the smaller rare‐earth elements (Nd–Lu), the bridging is entirely different, with two μ‐κ1(N):κ1(N) pyrazolate and two unusual bridging thf ligands. Each Ln atom also has two chelating Me2pz ligands, resulting in formal eight‐coordination. Crystallisation of [Nd(Me2pz)3(thf)]2 from pyridine yields monomeric, nine‐coordinate [Nd(Me2pz)3(pyridine)3] with only chelating Me2pz ligands.
Effects and mechanisms of 8‐prenylnaringenin on osteoblast MC3T3‐E1 and osteoclast‐like cells RAW264.7
Authors: Luo Dan , Kang Lumei , Ma Yuhui , Chen Hongping , Kuang Haibin , Huang Qiren , He Ming , Peng Weijie
Published: April 2014

8‐Prenylnaringenin (8‐PN) is a phytoestrogen with the highest estrogenic activity. The objective of the present study was to confirm the superiority of 8‐PN on bone metabolisms and the estrogen receptor (ER) subtype mediating effects of 8‐PN. The osteoblast MC3T3‐E1 and osteoclast‐like cell line RAW264.7 were treated with 17β‐estradiol (10−8 mol/L), genistein (10−5 mol/L), daidzein (10−5 mol/L), 8‐PN (10−5 mol/L) alone or in the presence of ERα antagonist MPP (10−7 mol/L) and ERβ antagonist PTHPP (1.5 × 10−7 mol/L). It has been found that 8‐PN did not affect osteoblast proliferation, and that 8‐PN increased alkaline phosphatase (ALP) activity, osteocalcin (OCN) concentrations, and the mineralized nodules. 8‐PN inhibited RAW264.7 differentiating into osteoclasts and reduced the pit area of bone resorption. 8‐PN could also inhibit the protein and mRNA expression of receptor activator of nuclear factor‐κB ligand (RANKL) in osteoblasts, and conversely promote the expression of osteoprotegerin (OPG). These effects of 8‐PN were mainly inhibited not by PTHPP but by MPP and they were weaker than estrogen's effects but stronger than those of genistein and daidzein. In conclusion, the effects of 8‐PN on promoting osteoblastic bone formation and inhibiting osteoclastic bone resorption were mediated by ERα instead of ERβ and the efficacy was more potent than that of the two classic phytoestrogens: genistein and daidzein.
Genomic profiling reveals distinctive molecular relapse patterns in IDH1/2 wild‐type glioblastoma
Authors: Riehmer Vera , Gietzelt Jens , Beyer Ulrike , Hentschel Bettina , Westphal Manfred , Schackert Gabriele , Sabel Michael C. , Radlwimmer Bernhard , Pietsch Torsten , Reifenberger Guido , Weller Michael , Weber Ruthild G. , Loeffler Markus ,   for the German Glioma Network
Published: April 2014

Molecular changes associated with the progression of glioblastoma after standard radiochemotherapy remain poorly understood. We compared genomic profiles of 27 paired primary and recurrent IDH1/2 wild‐type glioblastomas by genome‐wide array‐based comparative genomic hybridization. By bioinformatic analysis, primary and recurrent tumor profiles were normalized and segmented, chromosomal gains and losses identified taking the tumor cell content into account, and difference profiles deduced. Seven of 27 (26%) pairs lacked DNA copy number differences between primary and recurrent tumors (equal pairs). The recurrent tumors in 9/27 (33%) pairs contained all chromosomal imbalances of the primary tumors plus additional ones, suggesting a sequential acquisition of and/or selection for aberrations during progression (sequential pairs). In 11/27 (41%) pairs, the profiles of primary and recurrent tumors were divergent, i.e., the recurrent tumors contained additional aberrations but had lost others, suggesting a polyclonal composition of the primary tumors and considerable clonal evolution (discrepant pairs). Losses on 9p21.3 harboring the CDKN2A/B locus were significantly more common in primary tumors from sequential and discrepant (nonequal) pairs. Nonequal pairs showed ten regions of recurrent genomic differences between primary and recurrent tumors harboring 46 candidate genes associated with tumor recurrence. In particular, copy numbers of genes encoding apoptosis regulators were frequently changed at progression. In summary, approximately 25% of IDH1/2 wild‐type glioblastoma pairs have stable genomic imbalances. In contrast, approximately 75% of IDH1/2 wild‐type glioblastomas undergo further genomic aberrations and alter their clonal composition upon recurrence impacting their genomic profile, a process possibly facilitated by 9p21.3 loss in the primary tumor. © 2014 Wiley Periodicals, Inc.
Narrow band imaging of nasopharynx to identify specific features for possible detection of early nasopharyngeal carcinoma
Authors: Madana J. , Lim Chwee Ming , Loh Kwok Seng
Published: April 2014

Background

Narrow band imaging (NBI) features of normal and early nasopharyngeal carcinoma (NPC) have not been clearly described. The main purpose of this study was to define NBI features in the nasopharynx in the detection of early NPC.

Methods

We conducted a prospective cohort study of 53 patients who underwent NBI endoscopy to describe its specific features.

Results

Among 19 normal patients, common NBI features were discrete brown spots (100%) and regular polygonal follicular pattern of nasopharyngeal mucosa (90%). The features of 15 patients with NPC were loss of normal polygonal follicular architecture of nasopharynx (100%), concentrated brown spots (93%), and pale pink areas (80%). In the 19 post‐NPC radiation patients, common features were patches of intense brown‐green spots (100%), loss of polygonal follicular pattern of nasopharyngeal mucosa (95%), and discrete microvasculature branches (95%).

Conclusion

There are discernible NBI features between normal mucosa and an exophytic NPC mass. This can form the basis of a prospective screening program to detect early NPC using NBI. © 2014 Wiley Periodicals, Inc. Head Neck 37: 1096–1101, 2015
Expression profile and in vitro blockade of programmed death‐1 in human papillomavirus–negative head and neck squamous cell carcinoma
Authors: Malm Ian‐James , Bruno Tullia C. , Fu Juan , Zeng Qi , Taube Janis M. , Westra William , Pardoll Drew , Drake Charles G. , Kim Young J.
Published: April 2014

Background

Treatment with a blocking programmed death‐1 (αPD‐1) antibody recently showed clinical efficacy for various tumor types. In this study, we characterized the expression profile of PD‐1/programmed death‐ligand‐1 (PD‐L1) and the potential of PD‐1 blockade in human papillomavirus (HPV)‐negative head and neck squamous cell carcinoma (HNSCC).

Methods

Lymphocytes from peripheral blood, draining lymph nodes, and the tumor were phenotyped for PD‐1 expression, and their proliferative activity was assessed in the presence of blocking αPD‐1 treatment. Primary tumor expression of PD‐L1 was also analyzed using immunohistochemistry (IHC).

Results

Lymphocyte PD‐1 expression was abundant with highest expression in the tumor, and in vitro mixed lymphocyte reaction demonstrated that PD‐1 blockade could induce T cell proliferation. Furthermore, tumor cells were found to have 3 distinct patterns of PD‐L1 expression with over 78% of the specimens demonstrating strong PD‐L1 positivity.

Conclusion

Our data strongly supports the use of αPD‐1 blockade in patients with HPV‐negative HNSCC that are refractory to standard treatments. © 2014 Wiley Periodicals, Inc. Head Neck 37: 1088–1095, 2015
Norbornanoid Chiral Ketones by Desymmetrization of Dibromoalkenes
Authors: Koçak Ramazan , Borsato Giuseppe , De Lucchi Ottorino , Daştan Arif
Published: April 2014

New optically active polycyclic ketones 6a–6d, amenable to a large variety of synthetic applications, have been prepared from readily available 2,3‐dibromonorbornene and analogs (Scheme 2) via desymmetrization with (−)‐ephedrine, followed by hydrolysis under mild acidic conditions. At variance with substrates 4a–4d, the sterically hindered norbornene derivative 4e reacts with the solvent N‐methylpyrrolidin‐2‐one (NMP) leading to the formation of the unusual cyclopropanoid products 8a and 8b.