bluuebunny/crossref_metadata_2025_split huggingface dataset:
Theoretical Studies of the Asymmetric Binary‐Acid‐Catalyzed tert‐Aminocyclization Reaction: Origins of the CH Activation and Stereoselectivity
Authors: Zhang Long , Chen Liujuan , Lv Jian , Cheng Jin‐Pei , Luo Sanzhong 
Published: September 2012

AbstractA mechanistic study of the tert‐aminocyclization reaction was performed by using DFT calculations and labeling experiments. The results showed that the reaction proceeded through a rate‐limiting‐, stereospecific‐, and suprafacial 1,5‐H‐transfer pathway, followed by a barrier‐less CC bond formation. The mode of stereocontrol for facial selection could be ruled out owing to the high activation energy of CN bond rotation. The intrinsic feature of this Lewis acid activation was found to be the activation of the LUMO, as well as an intermediate‐stabilization effect. The catalytically active species was believed to be a 1:1 complex of phosphoric acid and MgCl2, which was stabilized by a H⋅⋅⋅Cl hydrogen bond. The chiral catalytic complex selectively recognizes and activates one of the two helical conformations of substrate A, required for 1,5‐suprafacial H‐transfer, which dictates the stereoselectivity of the forming products.
A methodology for schedule‐based paths recommendation in multimodal public transportation networks
Authors: Canca David , Zarzo Alejandro , González‐R Pedro L. , Barrena Eva , Algaba Encarnación 
Published: September 2012

SUMMARYThis paper analyzes the problem of intermodal itineraries recommendation in interurban networks where different public transportation modes, several companies, time, and capacity constraints, as well as seat booking, are considered. The inherent network optimization problem is first modeled for a generic user request, and then a solving method that makes use of a network graph transformation is proposed. For each request, this solving method is based on pruning the user‐specific time–space graph, followed by the application of a k‐shortest path algorithm. Moreover, in order to build on‐demand real‐time itineraries recommendations, the algorithm has been embedded in a Web client–server to which users ask for trip recommendations by Internet or mobile phone. Finally, as an illustration, the proposed approach has been tested on the Andalusia main transportation network. Copyright © 2012 John Wiley & Sons, Ltd.
Total Synthesis of Marine Eicosanoid (−)‐Hybridalactone
Authors: Ota Koichiro , Sugata Naoto , Ohshiro Yoshihiko , Kawashima Etsuko , Miyaoka Hiroaki 
Published: September 2012

Abstract(−)‐Hybridalactone (1) is a marine eicosanoid isolated from the red alga Laurencia hybrida. This natural product contains cyclopropane, cyclopentane, 13‐membered macrolactone and epoxide ring systems incorporating seven stereogenic centers. Moreover, this compound has an acid‐labile skipped Z,Z‐diene motif. In this paper, we report on the total synthesis of (−)‐hybridalactone (1). The unique eicosanoid (−)‐hybridalactone (1) was synthesized starting from optically active γ‐butyrolactone 2 in a linear sequence comprising 21 steps with an overall yield of 21.9 %. A key step in the synthesis of (−)‐hybridalactone (1) is the methyl phenylsulfonylacetate‐mediated one‐pot synthesis of the cis‐cyclopropane‐γ‐lactone derivative. This reaction provided an efficient and stereoselective access to cis‐cyclopropane‐γ‐lactone 12. Further elaboration of the latter compounds through desulfonylation, epoxidation, oxidation, Wittig olefination and Shiina macrolactonization afforded (−)‐hybridalactone.
Random Matrices and Complexity of Spin Glasses
Authors: Auffinger Antonio , Arous Gérard Ben , Černý Jiří 
Published: September 2012

AbstractWe give an asymptotic evaluation of the complexity of spherical p‐spin spin glass models via random matrix theory. This study enables us to obtain detailed information about the bottom of the energy landscape, including the absolute minimum (the ground state), and the other local minima, and describe an interesting layered structure of the low critical values for the Hamiltonians of these models. We also show that our approach allows us to compute the related TAPcomplexity and extend the results known in the physics literature. As an independent tool, we prove a large deviation principle for the kth‐largest eigenvalue of the Gaussian orthogonal ensemble, extending the results of Ben Arous, Dembo, and Guionnet. © 2012 Wiley Periodicals, Inc.
Improving the Capture of CO2 by Substituted Monoethanolamines: Electronic Effects of Fluorine and Methyl Substituents
Authors: Gangarapu Satesh , Marcelis Antonius T. M. , Zuilhof Han 
Published: September 2012

AbstractThe influence of electronic and steric effects on the reaction between CO2 and monoethanolamine (MEA) absorbents is investigated using computational methods. The pKa of the alkanolamine, the reaction enthalpy for carbamate formation, and the hydrolytic carbamate stability are important factors for the efficiency of CO2 capture. The steric and electronic effects of CH3, CH2F, CHF2, CF3, F, dimethyl, difluoro, and bis(2‐trifluoromethyl) substituents at the α carbon of MEA on this reaction are investigated. Density functional theory (DFT) (B3LYP, M06‐2X, M08‐HX and M11‐L) and ab initio methods [spin component‐scaled second‐order Møller‐Plesset theory (SCS‐MP2), G3], each coupled with solvent models [conductor‐like polarizable continuum model (CPCM) and universal solvation models (SM8 and SMD)], are shown to yield accurately calculated pKa values of the substituted MEAs. Specifically, G3, SCS‐MP2, and M11‐L methods coupled with the SMD and SM8 solvation models perform well with a mean unsigned error (MUE) of only 0.15, 0.24 and 0.25 pKa units, respectively. SCS‐MP2 is used to calculate the reaction enthalpy for carbamate formation and the carbamate stability towards hydrolysis. With the introduction of β‐fluoro substituents (especially the CH2F moiety) the reaction enthalpy for the formation of carbamates can be fine‐tuned to be less exothermic than that using the unsubstituted MEA. This implies a reduced energy requirement for the solvent‐regeneration step in the post‐combustion carbon‐capture method, which is currently the energy‐limiting step in efficient CO2 capture. β‐Fluoro‐substituted MEAs are also shown to form less stable carbamates than MEA. Thus, β‐fluoro‐substituted MEAs display a great potential for the use in the post‐combustion carbon‐capture process. Finally, a clear correlation is observed between the gas‐phase basicity and the tendency to form carbamates. This allows for the rapid prediction of which species will be formed experimentally, and thus the CO2‐absorbing capacities of alkanolamines can be estimated.
Radial Distributions of Dusty Plasma Parameters in a DC Glow Discharge
Authors: Sukhinin G. I. , Fedoseev A. V. 
Published: September 2012

AbstractA non‐stationary non‐local kinetic model for radial distributions of dusty plasma parameters based on the solution of Boltzmann equation for electron energy distribution function is presented. Electrons and ions production in ionizing collisions and their recombination on dust particle surface were taken into account. The drift‐diffusion approximation for ions was used. To obtain the self‐consistent radial distribution of electric potential the Poisson equation was used. It is shown that at high dust particle density the recombination of electrons and ions can exceed their production in ionization collisions in the region of dusty cloud. In this case the non‐monotonous radial distribution of the electric field is formed, the radial electric field becomes reversed and the radial electron and ion fluxes change their direction toward the center of the tube (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Vibrational Excitation of N2(B, C) and N+2(B) States in N2 and N2 – H2 Flowing Microwave Discharges
Authors: Abdeladim M. , Ricard A. , Mekkakia Maaza N. 
Published: September 2012

AbstractThe ro‐vibrational spectra of N2 microwave discharges have been analysed by emission spectroscopy. It is deduced the rotational and vibrational temperatures of N2 states. The characteristic of vibrational temperature Θ1 of the N2 (X, v) ground state has been specifically determined.It has been found that the N2 (C, B, v') and N+2 (B, v') radiative states are directly excited by electron collisions on the N2 (X,v) ground state at a N2 gas pressure of 0.1 Torr (discharge tube of 5 mm I.D, microwave power 100 Watt) with a Θ1 value near 104 K. At higher gas pressure up to 5 Torr, the N2 (C, v') states remain alone to be mainly excited by electron collisions on N2 (X, v). It is considered the excitations of the N2 (B, v') states by collisions of electrons and N2 (X,v > 4) vibrational molecules on the N2 (A) metastable states.With x < 9% H2 into N2, it is observed an increase of N2, 2nd pos intensity, resulting of an increase of high energy electrons. Inversely, the N2, 1st pos intensity decreased, partly following the decrease of low energy electrons (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Effects of Coupling Oscillations on the Electron Conductivity of Hall Thrusters
Authors: Wei L. , Han K. , Zhang Ch. , Yu D. 
Published: September 2012

AbstractIt is known that the static magnetic field of a Hall thruster remains unchanged with the product of coil current and coil turn kept constant. This is called the ampere‐turns equivalence principle, which is used in the static magnetic field design of Hall thrusters. It is found that the discharge characteristic is different with the same static magnetic field which is formed by the same ampere‐turns but different coil turns. The effects of the fluctuating magnetic field on the static magnetic field are studied experimentally and theoretically, and the effective collision frequency is calculated based on the dispersion relation of coupling oscillations and the estimation of the fluctuating magnetic field. Results indicate that the different coil turns are accompanied by different coupling intensities which lead to different magnetic field fluctuations. The different magnetic field fluctuations cause differences in the effective electron collision frequency and therefore the electron conductivity and the discharge characteristic of Hall thrusters (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Adaptive frame on binary splitting for radio frequency identification anticollision
Authors: Lai Yuan‐Cheng , Hsiao Ling‐Yen 
Published: September 2012

SUMMARYIn many radio frequency identification applications, the reader must repeatedly identify the same staying tags. Existing anticollision protocols, adaptive binary splitting (ABS) and adaptive query tree, can rapidly identify the staying tags by remembering the order in which the tags were recognized in the previous identification process. This paper proposes a novel protocol called adaptive frame ABS (AFA), based on ABS. AFA utilizes the dynamic regulation approach that estimates the numbers of staying tags and newly‐arriving tags and optimally adjusts the numbers of slots allocated for them to reduce idle slots when many recognized tags leave and reduce collision slots when many newly‐arriving tags enter. Following the regulation process, multiple staying tags may share the same slot and cause a collision among them. Thus, an efficient ordering splitting is proposed to deterministically split the collided staying tags according to the order in which they were recognized. The analytical and simulation results show that AFA outperforms ABS in most of the considered environments. Copyright © 2012 John Wiley & Sons, Ltd.
Direct displacement‐based seismic assessment procedure for multi‐span reinforced concrete bridges with single‐column piers
Authors: Şadan Oğuz Bahadır , Petrini Lorenza , Calvi Gian Michele 
Published: September 2012

ABSTRACTIn Italy, as in other high seismic risk countries, many bridges, nowadays deemed ‘strategic’ for civil protection interventions after an earthquake, were built without antiseismic criteria, and therefore their seismic assessment is mandatory. Accordingly, the development of a seismic assessment procedure that gives reliable results and, at the same time, is sufficiently simple to be applied on a large population of bridges in a short time is very useful.In this paper, a displacement‐based procedure for the assessment of multi‐span RC bridges, satisfying these requirements and called direct displacement‐based assessment (DDBA), is proposed. Based on the direct displacement‐based design previously developed by Priestley et al., DDBA idealizes the multi DOF bridge structure as an equivalent SDOF system and hence defines a safety factor in terms of displacement. DDBA was applied to hypothetical bridge configurations. The same structures were analyzed also using standard force‐based approach. The reliability of the two methods was checked performing IDA with response spectrum compatible accelerograms. Copyright © 2012 John Wiley & Sons, Ltd.
Carers' Assessment, Skills and Information Sharing: Theoretical Framework and Trial Protocol for a Randomised Controlled Trial Evaluating the Efficacy of a Complex Intervention for Carers of Inpatients with Anorexia Nervosa
Authors: Goddard Elizabeth , Raenker Simone , Macdonald Pamela , Todd Gillian , Beecham Jennifer , Naumann Ulrike , Bonin Eva‐Maria , Schmidt Ulrike , Landau Sabine , Treasure Janet 
Published: September 2012

AbstractExperienced Carers Helping Others (ECHO) is a guided self‐help intervention for carers of people with eating disorders to reduce distress and ameliorate interpersonal maintaining factors to improve patient outcomes. The aim of this paper is to describe the theoretical background and protocol of a randomised controlled trial that will establish whether ECHO has a significant beneficial effect for carers and the person they care for. Individuals with anorexia nervosa and carers will be recruited from eating disorder inpatient/day patient hospital services in the UK. Primary outcomes are time until relapse post‐discharge (patient) and distress (carer) at 12 months post‐discharge. Secondary outcomes are body mass index, eating disorder symptoms, psychosocial measures and health economic data for patients and carers. Carers will be randomised (stratified by site and illness severity) to receive ECHO (in addition to treatment as usual) or treatment as usual only. Potential difficulties in participant recruitment and delivery of the intervention are discussed. Copyright © 2012 John Wiley & Sons, Ltd and Eating Disorders Association.
TRULY INEFFICIENT OR PROVIDING BETTER QUALITY OF CARE? ANALYSING THE RELATIONSHIP BETWEEN RISK‐ADJUSTED HOSPITAL COSTS AND PATIENTS' HEALTH OUTCOMES
Authors: Gutacker Nils , Bojke Chris , Daidone Silvio , Devlin Nancy J. , Parkin David , Street Andrew 
Published: September 2012

ABSTRACTObserved variation in hospital costs may be attributable to differences in patients' health outcomes. Previous studies have resorted to inherently incomplete outcome measures such as mortality or re‐admission rates to assess this claim. This study makes use of a novel dataset of routinely collected patient‐reported outcome measures (PROMs) linked to inpatient records to (i) access the degree to which cost variation is associated with variation in patients' health gain and (ii) explore how far judgement about hospital cost performance changes when health outcomes are accounted for. We use multilevel modelling to address the clustering of patients in providers and isolate unexplained cost variation. We find some evidence of a U‐shaped relationship between risk‐adjusted costs and outcomes for hip replacement surgery. For three other procedures (knee replacement, varicose vein and groin hernia surgery), the estimated relationship is sensitive to the choice of PROM instrument. We do not observe substantial changes in cost performance estimates when outcomes are explicitly accounted for. Copyright © 2012 John Wiley & Sons, Ltd.
Early‐stage squamous cell carcinoma of the lip: The Australian experience and the benefits of radiotherapy in improving outcome in high‐risk patients after resection
Authors: Najim Maria , Cross Shamira , Gebski Val , Palme Carsten E. , Morgan Gary J. , Veness Michael J. 
Published: September 2012

BackgroundThe purpose of this study was to analyze the outcome of Australian patients treated for early lip cancer.MethodsData on 217 patients with T1 to T2 squamous cell carcinoma (SCC) of the lip and treated with radical intent were analyzed.ResultsThe addition of local adjuvant radiotherapy in patients with a close/positive margin was associated with a significant improvement in relapse‐free survival (RFS; p = .008). Tumor thickness (≤4 mm vs >4 mm) was also significantly associated with RFS (p = .01). The 5‐year RFS was 51% after surgery, 87% after radiotherapy, and 92% after adjuvant radiotherapy.ConclusionsPatients with a tumor thickness >4 mm experienced an increased risk of recurrence, especially nodal. Compared with patients having any radiotherapy, those undergoing surgery experienced a higher rate of locoregional recurrence. The addition of adjuvant radiotherapy in patients with inadequate excision significantly decreased the risk of recurrence. © 2012 Wiley Periodicals, Inc. Head Neck 35: 1426–1430, 2013
Transcriptome alterations induced by cigarette smoke
Authors: Brody Jerome S. 
Published: September 2012

AbstractCigarette smoke alters the transcriptome of multiple tissues; those directly exposed to toxic products and those exposed to circulating components and metabolic products of tobacco smoke. In most tissues and organs that have been studied, the smoking transcriptome is characterized by increased expression of antioxidant and xenobiotic genes as well as a wide spectrum of inflammation‐related genes, and potential oncogenic genes. Smoking is associated with an increased incidence of cancer in a number of organs both those directly exposed (lungs and airways) and those indirectly exposed (bladder, liver, pancreas). Individual transcriptomic responses vary, based to some degree on as yet to be clarified genetic factors, and likely how and what the individual has smoked. The complexity of individual responses to tobacco exposure and of smoking‐related cancers in various organs is beginning to be revealed in transcriptomic and whole genome sequencing studies, of both tumors and cytologically normal appearing cells that have been exposed to cigarette smoke or its products creating a genomic “field of injury.” The recent application of next generation sequencing to defining the transcriptome alterations induced by cigarette smoke holds the promise of discovering new approaches to personalized prevention and treatment of smoking‐related lung diseases in the future.
Tyrosine kinase inhibitor (TKI)‐induced cardiotoxicity: approaches to narrow the gaps between preclinical safety evaluation and clinical outcome
Authors: Yang Baichun , Papoian Thomas 
Published: September 2012

ABSTRACTAlthough therapies targeted to inhibit the activity of certain tyrosine kinases (TK) have helped advance cancer therapy in recent years, reports of cardiac toxicity following treatment with tyrosine kinase inhibitors (TKIs) were unexpected and not well predicted by preclinical studies. Such clinical findings exposed gaps in current preclinical drug testing for predicting the development of cardiac toxicities in humans. These gaps included a lack of a comprehensive TKI mechanism of action determination and appropriate cardiac functional evaluation. New preclinical approaches are suggested to address these issues. In addition to tyrosine kinase inhibition, other factors that may play a role in drug‐induced cardiac effects should be assessed, such as unintended secondary targets of TKIs, toxic drug metabolites and drug accumulation in the heart. Both on‐target and off‐target toxic effects of TKIs on cultured cardiac myocytes have now been shown to be detectable, providing a rationale for using cardiomyocytes as a screening tool to study potential TKI‐mediated cardiotoxicity. Incorporating isolated perfused heart methodology to chronic/subchronic rodent studies or including echocardiography in chronic large animal toxicity studies may improve the detection of changes in cardiac function over current methods, and they may eventually become a routine tool for screening drugs with suspected cardiotoxic potential. Further, assessing drug toxicity and efficacy together in an animal model of disease is highly informative for candidate drug selection, and should be encouraged to assess specific safety endpoints, such as cardiovascular function. Together, these approaches will help better close the gaps between preclinical testing and clinical outcomes. Published 2012. This article is a U.S. Government work and is in the public domain in the USA.
MISSION DRIFT OR STRATEGIC SHIFT? GROUP FORMATION STRATEGIES WITHIN MEPs
Authors: Chu Vien , Luke Belinda 
Published: September 2012

AbstractMission drift is a common criticism of microenterprise programs (MEPs) that target those likely to succeed rather than those most in need. This note examines approaches to group formation within international NGOs operating MEPs in Vietnam. A deliberate strategy of involving both poor and non‐poor households in MEPs emerges through effectuation, learning from past challenges. This approach represents a shift in focus away from the extremely poor but presents a potential pathway for effective and sustainable poverty alleviation, if undertaken as part of an integrated program. Copyright © 2012 John Wiley & Sons, Ltd.
Extranodal natural killer/T‐cell lymphoma, nasal type: Clinical and computed tomography findings in the head and neck region
Authors: Hung Liang‐Yueh , Chang Po‐Hung , Lee Ta‐Jen , Hsu Yin‐Ping , Chen Yi‐Wei , Fu Chia‐Hsiang , Huang Chi‐Che 
Published: September 2012

AbstractObjectives/Hypothesis:In patients with nasal natural killer/T‐cell lymphoma (NKTL), it is commonly without an obvious mass found in the nasal cavity by clinical or computed tomography (CT) findings. As a result, it takes longer to make a definite diagnosis when compared with other nasal malignancy. This study was designed to investigate clinical and CT findings of nasal NKTL.Study Design:Forty‐three patients with nasal NKTL were enrolled. The patients' data were collected retrospectively.Methods:All patients underwent contrast‐enhanced CT scans and endoscopic examinations. Symptoms were noted and recorded in detail.Results:Patients with lymphoma limited to their nasal cavity or paranasal sinus (N/PN) presented symptoms similar to chronic rhinosinusitis, such as nasal obstruction and purulent nasal discharge. Patients with lymphoma of the nasopharynx or oropharynx (NPx/OPx) tended to present more frequently with epistaxis or blood‐tinged sputum. On CT, NKTL was usually nonenhanced (79.1%), homogenous (100%), unilateral (61.9%), infiltrative (67.4%), and without central necrosis. Only 30.2% of the patients presented with a prominent mass. One disease‐specific sign, different from patients with chronic rhinosinusitis, was that the mucosa of the nasal cavity was thickened without involvement of the mucosa of the paranasal sinus (40.6%).Conclusions:The thickening of the mucosa of the nasal cavity without similar involvement of the paranasal sinuses is easily overlooked in patients with NKTL. In addition, the imaging findings of thickened mucosa of the nasal floor and/or nasal septum near the inferior meatus, a prominent mass, and bony destruction should raise suspicion of this diagnosis. Laryngoscope, 2012