bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mechanistic Investigation of Organolanthanide‐Mediated Hydroamination of Conjugated Aminodienes: A Comprehensive Computational Assessment of Various Routes for Diene Activation
Authors: Tobisch Sven 
Published: October 2010

AbstractThe present computational mechanistic study comprehensively explores alternative scenarios for activation of the amine‐linked diene CC linkage toward CN ring closure in intramolecular hydroamination of a prototypical aminodiene by a well‐characterised lanthanocene–amido catalyst. Firstly, the non‐insertive mechanism by Scott featuring ring closure with concomitant amino proton delivery onto the diene unit has been explored and key features have been defined. This scenario has been compared with the classical stepwise insertion mechanism that involves rapid substrate association/dissociation equilibria for the 3 t‐S1 resting state and also for azacycle intermediates 4 s, 4 a, facile and reversible exocyclic migratory diene insertion into the LaN(amido) σ‐bond, linked to turnover‐limiting LaC azacycle aminolysis. The LnN σ‐bond insertive mechanism prevails for the examined intramolecular hydroamination of (4E,6)‐heptadienylamine 1 t by [Cp*2LaCH(TMS)2] starting material 2.The following aspects are in support of this mechanism: 1) the derived rate law is consistent with the observed empirical rate law; 2) the assessed effective barrier for turnover‐limiting aminolysis does agree remarkably well with empirically determined Eyring parameters; 3) the ring‐ether double‐bond selectivity is consistently elucidated. This study reveals that the non‐insertive mechanism is not achievable for the particular lanthanocene–amido catalyst and furthermore cannot account for the observed product spectrum. Notwithstanding of these findings, the non‐insertive mechanism cannot be discarded a priori for intramolecular aminodiene hydroamination. Spatial demands around the lanthanide centre influence the two mechanisms differently. The LnN σ‐bond insertive mechanism critically relies on a sufficiently accessible lanthanide and enhanced encumbrance renders cyclisation and aminolysis steps less accessible kinetically. It contrasts with the non‐insertive mechanism, where greater lanthanide protection has a rather modest influence. The present study indicates that the non‐insertive mechanism would prevail if the lanthanide centre were to be protected effectively against CC bond approach. Notably, a different product spectrum would be expected for aminodiene hydroamination following the insertive or non‐insertive route.
Atomistic In Situ Investigation of the Morphogenesis of Grains during Pressure‐Induced Phase Transitions: Molecular Dynamics Simulations of the B1–B2 Transformation of RbCl
Authors: Zahn Dirk , Tlatlik Harald 
Published: October 2010

AbstractThe mechanistic details of the pressure‐induced B1–B2 phase transition of rubidium chloride are investigated in a series of transition path sampling molecular dynamics simulations. The B2→B1 transformation proceeds by nucleation and growth involving several, initially separated, nucleation centers. We show how independent and partially correlated nucleation events can function within a global mechanism and explore the evolution of phase domains during the transition. From this, the mechanisms of grain boundary formation are elaborated. The atomic structure of the domain–domain interfaces fully support the concept of Bernal polyhedra. Indeed, the manifold of different grain morphologies obtained from our simulations may be rationalized on the basis of essentially only two different kinds of Bernal polyhedra. The latter also play a crucial role for the B1→B2 transformation and specific grain boundary motifs are identified as preferred nucleation centers for this transition.
Host–Guest Inclusion Compound from Nitramine Crystals Exposed to Condensed Carbon Dioxide
Authors: Saint Martin Sabine , Marre Samuel , Guionneau Philippe , Cansell François , Renouard Joel , Marchetto Virginie , Aymonier Cyril 
Published: October 2010

AbstractHNIW or CL20 (2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane) is a nitramine, which is considered as the highest energetic molecular compound known to date, therefore, attracting increasing interest in propulsion applications. Additionally, CL20 is an interesting system for fundamental studies, exhibiting several polymorphs, which can behave as host lattices for trapping guest molecules. Herein, a new CL20 structure that contains inserted CO2 molecules is reported. A combination of Fourier transform infra red (FTIR) spectroscopy, scanning electron microscopy (SEM), single‐crystal X‐ray diffraction, and thermal analyses (thermogravimetric analysis coupled with mass spectrometry and differential scanning calorimetry) was used to characterize this new material.
Molecular Alloys: Experimental and Theoretical Investigations on the Substitution of Zinc by Cadmium and Mercury in the Homologous Series [Mo(M′R)12] and [M(M′R)8] (M=Pd, Pt; M′=Zn, Cd, Hg)
Authors: Bollermann Timo , Cadenbach Thomas , Gemel Christian , von Hopffgarten Moritz , Frenking Gernot , Fischer Roland A. 
Published: October 2010

AbstractThe synthesis and structural characterization of novel, metal‐rich, highly coordinated compounds [Mo(M′R)12] and [M(M′R)8] (M: Pd, Pt, Mo; M′: Zn, Cd; R: Me=CH3, Cp*=pentamethylcyclopentadienyl) are reported. Additionally, a description of the bonding situation of the new compounds by means of quantum‐chemical calculations is presented including the Hg analogues. Reaction of [Pt(GaCp*)4] with CdMe2results in the formation of the unprecedented all‐Cd coordinated [Pt(CdMe)4(CdCp*)4] (1). Similarly, the treatment of the all‐Zn coordinated [Pd(ZnMe)4(ZnCp*)4] with CdMe2affords the novel Zn/Cd mixed compound [Pd(CdMe)4(ZnCp*)4] (2). The related Zn/Cd mixed compound [Mo(ZnCp*)3(CdMe)9] (3) is prepared by reaction of [Mo(ZnCp*)4(GaMe)4] with an excess amount of CdMe2. All compounds were analyzed by1H and13C NMR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction. The bonding situation of these highly coordinated, metal‐rich molecules1–3were studied by quantum‐chemical calculations using density functional theory (DFT) at the BP86/TZ2P+ level, atoms‐in‐molecules (AIM) analysis, and energy‐decomposition analysis (EDA), as well as the its natural orbitals for chemical valence variation (EDA‐NOCV) and including the hypothetically all‐Hg‐coordinated analogues. The results point out that the radial interactions M–M′ in the icosahedral compounds that have twelve ligands are best described as classical electron‐pair‐sharing covalent bonds, whereas the dodecahedral species, which have eight ligands, exhibit metal–ligand donor–acceptor bonds. The attractive interactions between the metal–ligand fragments M′R by means of M′–M′ bonds are weaker but not insignificant. All complexes fulfill the 18‐electron rule. The analysis clarifies the electronic structures as being distinctly different from typical endohedral clusters M@(M′′R)nthat exhibit strong peripheral M′′–M′′ interactions: The M′M′ bonds are not strong enough to yield stable (M′R)ncages.
Narratives of irony and failure in ethnographic work
Authors: Jemielniak Dariusz , Kostera Monika 
Published: October 2010

AbstractOrganizational ethnography is one of the most valued approaches to qualitative studies of organizations. Much attention has been given to the development of the research process, of which the researcher's identity is an integral part. However, we believe that the analysis of research failures has been much less developed in the discourse of ethnographic methods for the study of organizations. Therefore, we have explored some of the “slips” in ethnographic work, as described in accounts of fellow organizational anthropologists. As the study is qualitative, we have adopted a narrative research method. We have divided the “slips” (i.e., errors) into four categories important for the ethnographer's identity: (a) one's role; (b) one's project, (c) one's relation to “the Other”; and (d) the social context of the slip. Copyright © 2010 ASAC. Published by John Wiley & Sons, Ltd.
The association of race/ethnicity, insurance status, and socioeconomic factors with breast cancer care
Authors: Freedman Rachel A. , Virgo Katherine S. , He Yulei , Pavluck Alexandre L. , Winer Eric P. , Ward Elizabeth M. , Keating Nancy L. 
Published: October 2010

AbstractBACKGROUND:Few data are available on how race/ethnicity, insurance, and socioeconomic status (SES) interrelate to influence breast cancer treatment. The authors examined care for a national cohort of breast cancer patients to assess whether insurance and SES were associated with racial/ethnic differences in care.METHODS:The authors used multivariate logistic regression to assess the probability of definitive locoregional therapy, hormone receptor testing, and adjuvant systemic therapy among 662,117 white, black, and Hispanic women diagnosed with invasive breast cancer during 1998‐2005 at National Cancer Data Base hospitals. In additional models, the authors included insurance and area‐level SES to determine whether these variables were associated with observed racial/ethnic disparities.RESULTS:Most women were white (86%), 10% were black, and 4% were Hispanic. Most had private insurance (51%) or Medicare (41%). Among eligible patients, 80.0% (stage I/II) had definitive locoregional therapy, 98.5% (stage I‐IV) had hormone receptor testing, and 53.1% and 50.2% (stage I‐III) received adjuvant hormonal therapy and chemotherapy, respectively. After adjustment, black (vs white) women had less definitive locoregional therapy (odds ratio [OR], 0.91; 95% confidence interval [CI], 0.88‐0.94), hormonal therapy (OR, 0.90; 95% CI, 0.87‐0.93), and chemotherapy (OR, 0.87; 95% CI, 0.84‐0.91). Hispanic (vs white) women were also less likely to receive hormonal therapy. Hormone receptor testing did not differ by race/ethnicity. Racial disparities persisted despite adjusting for insurance and SES.CONCLUSIONS:The modest association between black (vs white) race and guideline‐recommended breast cancer care was insensitive to adjustment for insurance and area‐level SES. Further study is required to better understand disparities and to ensure receipt of care. Cancer 2011. © 2010 American Cancer Society.
A review and characterization of the various perceptions of quality cancer care
Authors: Colosia Ann D. , Peltz Gerson , Pohl Gerhardt , Liu Esther , Copley‐Merriman Kati , Khan Shahnaz , Kaye James A. 
Published: October 2010

AbstractBACKGROUND:It is important to maintain high‐quality cancer care while reducing spending. This requires an understanding of how stakeholders define “quality.” The objective of this literature review was to understand the perceptions patients, physicians, and managed care professionals have about quality cancer care, especially chemotherapy.METHODS:A computerized literature search was conducted for articles concerning quality cancer care in patients who received chemotherapy. Among >1100 identified sources, 25 presented interviews/survey results from stakeholders.RESULTS:Patients defined quality cancer care as being treated well by providers, having multiple treatment options, and being part of the decision‐making process. Waiting to see providers, having problems with referrals, going to different locations for treatment, experiencing billing inaccuracies, and navigating managed care reimbursement negatively affected patients' quality‐of‐care perceptions. Providers perceived quality cancer care as making decisions based on the risks‐benefits of specific chemotherapy regimens and patients' health status rather than costs. Providers objected to spending substantial time interacting with payers instead of delivering care to patients. Payers must control the costs of cancer care but do not want an adversarial relationship with providers and patients. Payers' methods of managing cancer more efficiently involved working with providers to develop assessment and decision‐assist tools.CONCLUSIONS:Delivering quality cancer care is increasingly difficult because of the shortage of oncologists and rising costs of chemotherapy agents, radiation therapy, and imaging tests. The definition of quality cancer care differed among stakeholders, and healthcare reform must reflect these various needs to maintain and improve quality while controlling costs. Cancer 2011. © 2010 American Cancer Society
Replicating real‐time garbage collector
Authors: Kalibera Tomas 
Published: October 2010

AbstractReal‐time Java is becoming a viable platform for real‐time applications, bringing new challenges to a garbage collector. A real‐time collector has to be incremental as not to cause deadline misses by suspending an application for too long. In particular, if a real‐time collector has to relocate objects in the heap, it must do so incrementally and transparently to the application. This is usually achieved via an indirection that has to be followed on every read and write to the heap. We present an alternative solution, based on object replication, which does not need any special handling for memory reads, but writes are more expensive: every value is written twice. As writes are less frequent than reads, the total overhead is reduced. With our implementation in a research real‐time Java VM and DaCapo, pseudo‐jbb, and SPEC JVM 98 benchmarks, we observe an average speed‐up of 4% on a Linux/x86 platform. Compared with an existing technique for parallel systems, our technique targets uni‐processor green‐threading embedded systems, allowing us to design simpler and more predictable mutator barriers. Thanks to cheap synchronization provided by green threading, our technique features atomic writes to object replicas, providing programmers with the natural behavior in face of unprotected access to shared variables. Copyright © 2010 John Wiley & Sons, Ltd.
Anion‐Dependent Tendency of Di‐Long‐Chain Quaternary Ammonium Salts to Form Ion Quadruples and Higher Aggregates in Benzene
Authors: Rocchigiani Luca , Bellachioma Gianfranco , Ciancaleoni Gianluca , Crocchianti Stefano , Laganà Antonio , Zuccaccia Cristiano , Zuccaccia Daniele , Macchioni Alceo 
Published: October 2010

AbstractThe self‐aggregation tendency of [N(CH3)2(C18H37)2]X [1X; X−=BF4−, PF6−, OTf−, NTf2−, BPh4−, BTol4−, BArF−, and B(C6F5)4−] salts to form ion quadruples (IQs) and higher aggregates (HAggs) in [D6]benzene is investigated by means of diffusion NMR spectroscopy. The experimental results indicate that salts containing small anions (1BF4, 1PF6, and 1OTf) are present in solution as IQs even at the lowest investigated concentration of C=5×10−5 M and show a limited tendency to further self‐aggregate, reaching a maximum average aggregation number (N=VH/${V_{\rm{H}}^{{\rm{0IP}}} }$, where VH=measured hydrodynamic volume and ${V_{\rm{H}}^{{\rm{0IP}}} }$=hydrodynamic volume of the ion pair) of about 6–8 (C=0.050–0.100 M). Salts with larger counterions [1BPh4, 1BTol4, 1BArF, and 1B(C6F5)4] form instead ion pairs at low concentration but steadily self‐aggregate (especially the non‐fluorinated ones) on increasing their concentration up to N values exceeding 50 (C=0.030–0.050 M). 1NTf2 behaves in an intermediate fashion. The self‐aggregation tendency of salts is quantified by formulating the dependence of VH on C by means of the equations of indefinitive aggregation models. The following rankings for the formation of IQs and HAggs are obtained: IQs: 1BF4≈1PF6≈1OTf> 1NTf2>1B(C6F5)4≥1BPh4≥1BTol4≥1BArF; HAggs: 1BTol4>1BPh4> 1NTf2>1B(C6F5)4> 1BArF>1BF4≈1PF6≈1OTf. Interionic NOE NMR studies and DFT calculations were conducted in order to determine the relative anion–cation orientation in the self‐aggregating units.
Preparation and characterization of Bi0.9M0.05N0.05FeO3(M = Sm, Gd; N = Sr, Y) polycrystalline multiferroic compounds
Authors: Al‐Haj M. 
Published: October 2010

AbstractThe multiferroic compounds Bi0.9Gd0.05Sr0.05FeO3, Bi0.9Sm0.05Sr0.05FeO3, Bi0.9Gd0.05Y0.05FeO3, and Bi0.9Sm0.05Y0.05FeO3 were prepared by the conventional ceramic method and were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, vibrating sample magnetometry, and differential scanning calorimetry. The compounds were found to have the rhombohedral perovskite‐like structure, accompanied by the existence of small amounts of Bi2Fe4O9 and Bi25FeO40 impurity phases. The appearance of weak ferromagnetism in Bi0.9Gd0.05Sr0.05FeO3 and Bi0.9Sm0.05Sr0.05FeO3 is due to partial destruction of the spiral spin structure due to lattice distortion and oxygen vacancies. The magnetic transition temperatures of the compounds are 360 °C and 355 °C, respectively. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Microwave dielectric properties of La(1‐2x/3)Bax(Mg0.5Sn0.5)O3 ceramics
Authors: Chen Yih‐Chien , Chen Kuei‐Chien , Hsu Wei‐Yu 
Published: October 2010

AbstractThis study examined the potential applications of microwave dielectric properties of La(1‐2x/3)Bax(Mg0.5Sn0.5)O3 ceramics in rectenna. The La(1‐2x/3)Bax(Mg0.5Sn0.5)O3 ceramics were prepared by the conventional solid‐state method with various sintering temperatures. An apparent density of 6.62 g/cm3, a dielectric constant of 20.3, a quality factor of 51,700 GHz, and a temperature coefficient of resonant frequency of ‐78.2 ppm/K were obtained for La2.98/3Ba0.01(Mg0.5Sn0.5)O3 ceramics that were sintered at 1550 °C for 4 h. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Do mediators walk their talk in civil cases?
Authors: Wall James A. , Chan‐Serafin Suzanne 
Published: October 2010

AbstractIn this article we examine initial joint sessions in civil case mediations and note that, although understudied, they are a key element in the mediation process. Here mediators can set the tone of the mediation by delineating the goals, proffering advice to the disputants, and relating their experiences. They can indicate which strategy or style they will subsequently use. To investigate these aspects, we observed one hundred civil case mediations and found that mediators in the opening joint sessions typically did provide goals, advice, and descriptions. In about one‐half of the mediations, the mediators stated which style—neutral, evaluative, or pressing—they would use. Observations of the subsequent mediations revealed that mediators who said they would employ a neutral style seldom did so, whereas the mediators who said they would evaluate or press were more apt to follow their espoused strategy. An examination of the agreements in the mediations revealed that the evaluative strategy was most often associated with agreement, the pressing style was a close second, and the neutral style was a distant third. Moreover, it was noted that the evaluative and pressing mediators who walked their talk—who employed the strategy they said they would use—were effective in getting agreements. In contrast, the lowest number of agreements came when mediators initially stated they would use an evaluative strategy but subsequently pressed the disputants.
Fairness, understanding, and satisfaction: Impact of mediator and participant race and gender on participants' perception of mediation
Authors: Charkoudian Lorig , Kabcenell Wayne Ellen 
Published: October 2010

AbstractThis empirical study explores the effects of matching mediators and mediation participants by gender and by racial or ethnic identity group. It considers both the effect on a participant of being present in a mediation session where there is no mediator of the same gender or racial/ethnic group and the effect of being present when there is also a mediator who matches the gender or race/ethnicity of the other participant. The results show that failing to match disputants and mediators by gender has negative effects on mediation satisfaction measures and that those effects increase when the mediator's gender also matches that of the other participant. In contrast, failure to match by racial or ethnic group has little effect, but when an unmatched participant faces both an opposing participant and a mediator who share a racial or ethnic identification, mediation satisfaction decreases in several respects.
The culture of China's mediation in regional and international affairs
Authors: (Jason) Qian Cheng 
Published: October 2010

AbstractCurrently there seems to be an increasing interest in and demand for China's mediation in resolving conflict. To a certain extent, such a phenomenon is associated with China's re‐emerging power. But more importantly, it is probably the style and skills of China's mediation that matters, which represents the emerging of a unique mediation culture, with China being its messenger. The paper examines key elements of such a mediation culture, using examples of China's mediation in regional and international affairs. The shaping of such a culture offers good lessons for mediators around the world who strive for effective conflict resolution.
Ken Wilber's Integral Theory applied to mediation
Authors: Perloff Fred 
Published: October 2010

AbstractIntegral Theory is a metatheory developed by American philosopher Ken Wilber to include and contextualize all existing knowledge. This article uses Wilber's concepts of quadrants and levels to understand the goals and theoretical assumptions of six mediation approaches: evaluative, facilitative, humanistic, narrative, systemic, and transformative. The contributions to mediation from the modern, postmodern, and integral (post‐postmodern) levels of development are described. Some ways to recognize the diverse levels of mediation participants are offered, and several implications for mediators of Integral Theory are explored.
Efficient implementation of pseudochaotic piecewise linear maps with high digitization accuracies
Authors: Addabbo Tommaso , De Caro Davide , Fort Ada , Petra Nicola , Rocchi Santina , Vignoli Valerio 
Published: October 2010

SUMMARYIn this paper we discuss the efficient implementation of pseudochaotic piecewise linear maps with high digitization accuracies, taking the R'enyi chaotic map as a reference. The proposed digital architectures are based on a novel algorithmic approach that uses carry save adders for the nonlinear arithmetic modular calculations arising when computing piecewise linear maps with a finite precision. As a result, the system can be implemented by digital circuits obtaining high throughputs, which are not dependent on the digital resolution while involving a hardware complexity linearly proportional to the number of bits used for representing the discretized state. The proposed solutions result to be particularly suitable for the implementation of pseudorandom number generators based on pseudochaos, or for the definition of efficient digital blocks that can be integrated in most of the pseudochaotic cyphers proposed in the literature. Copyright © 2010 John Wiley & Sons, Ltd.
On the design of multi notch filters
Authors: Deshpande Rohini , Kumar B. , Jain S. B. 
Published: October 2010

SUMMARYA methodology for designing FIR multi notch filters (NFs) derived from second‐order prototype IIR NFs is suggested. Rejection bandwidth for the designed filter can be controlled by suitable choice of ‘r’, the pole radius of the IIR prototype NFs. The suggested multi NF can also be adapted to eliminate second‐, third‐ and fourth‐order harmonics of periodic noise besides the fundamental noise frequency component. A special case when two notch frequencies ω1 and ω2 are such that [(cosω1)(cosω2) = − 1/2] has also been discussed. The IIR multi NF design for this special case results in reduction of the number of multipliers without affecting the response of the desired NF. For the aforereferred condition, the required coefficients of impulse response of FIR multi notch filter get reduced to almost half in number resulting in reduced computations. The number of zero coefficients further reduces with increase in ‘r’ value. In addition, the frequency response becomes better, with reduced ripples in the pass bands, when ‘r’ is increased and length ‘L’ of the FIR NF is chosen appropriately. Copyright © 2010 John Wiley & Sons, Ltd.