bluuebunny/crossref_metadata_2025 huggingface dataset:
Effect of water activity on the lipase catalyzed esterification of geraniol in ionic liquid [bmim]PF6
Authors: Barahona Donifan , Pfromm Peter H. , Rezac Mary E.
Published: September 2005

Enzymatic reactions in non‐aqueous media have been shown to be effective in carrying out chemical transformation where the reactants are insoluble in water or water is a byproduct limiting conversion. Ionic liquids, liquid organic salts with infinitesimal vapor pressure, are potentially useful alternatives to organic solvents. It is known that the thermodynamic water activity is an important variable affecting the activity of enzymes in non‐aqueous solvents. This study investigated the influence of water activity on the esterification of geraniol with acetic acid in ionic liquid [bmim]PF6 catalyzed by immobilized Candida antarctica lipase B. The conversion of geraniol in [bmim]PF6 was significant although the reaction rate was slower than in organic solvents. The profile of initial reaction rate‐water activity was determined experimentally, and differed from the data reported for other non‐aqueous solvents. A maximum in the initial reaction rate was found at aw = 0.6. The pseudo reaction equilibrium constant, Kx, was measured experimentally for the reaction. The average value of Kx in [bmim]PF6 was 12, 20‐fold lower than the value reported for the same system in hexane. © 2005 Wiley Periodicals, Inc.
Synthesis of 9‐ and 27‐Armed Tetrakis(diperoxotungsto)phosphate‐Cored Dendrimers and Their Use as Recoverable and Reusable Catalysts in the Oxidation of Alkenes, Sulfides, and Alcohols with Hydrogen Peroxide
Authors: Nlate Sylvain , Plault Lauriane , Astruc Didier
Published: September 2005

A series of 3‐ and 9‐armed dendrons, functionalized at the focal position to quaternary ammonium salts, were synthesized and characterized. The reaction of these ammonium dendrons with the heteropolyacid H3PW12O40 in the presence of hydrogen peroxide led to a family of 9‐ and 27‐armed air‐stable polyoxometalate (POM)‐cored dendrimers containing a catalytically active trianionic POM species [PO4{WO(O2)2}4]3− in the core. These POM‐cored dendrimers are air‐stable, efficient, recoverable, and reusable catalysts for the selective oxidation of alkenes to epoxides, sulfides to sulfones, and alcohols to ketones, in an aqueous/CDCl3 biphasic system with hydrogen peroxide as the primary oxidant. A study of the countercation effects showed that the dendritic structure increased the stability of the POM species and facilitated the recovery of the catalyst up to the eighth cycle, whereas the increased bulkiness around the POM center led to a negative kinetic dendritic effect. Within the 9‐armed POM‐cored dendrimer series, the reaction kinetics were susceptible to the nature of the peripheral endgroups. Indeed, the 9‐armed n‐propyl‐terminated POM‐cored dendrimer was identified as the most active catalyst. In addition, the results obtained with POM‐cored dendrimers versus tetraalkylammonium POMs ({[n‐(C8H17)3NCH3]+}3[PO4{WO(O2)2}4]3− and [{nC18H37(75 %) + nC16H33(25 %)]2N(CH3)2}+]3[PO4{WO(O2)2}4]3−) clearly reveal that the dendritic structures are more stable than their nondendritic counterparts. After the reactions were complete, the dendrimer catalysts were easily recovered and recycled without a discernable lost of activity, whereas attempts to recover tetraalkylammonium POMs gave unsatisfactory results. A significant advantage of the dendritic structures is that they enable the recovery and recyclability of the POM catalyst, in contrast to the other tetraalkylammonium POMs.
Concise Approach to the “Higher Sugar” Core of the Nucleoside Antibiotic Hikizimycin
Authors: Fürstner Alois , Wuchrer Margarita
Published: September 2005

A highly productive synthesis of phenylthio glycoside 33 is described which constitutes a fully functional surrogate for the hikosamine core of hikizimycin 1, a complex nucleoside antibiotic endowed with promising anthelmintic properties. The chosen approach to this undecose derivative starts from mannofuranose 7 which was one‐carbon homologated to alkyne 8 in one step on treatment with lithio (trimethylsilyl)diazomethane. Alkynyl iodide 12 derived from 8 was combined with the tartrate‐derived aldehyde 17 by a Nozaki–Hiyama–Kishi reaction that can either be performed using overstoichiometric amounts of CrCl2 or by means of a catalytic manifold based on the turnover of a cat. CrCl2/chlorosilane/manganese redox couple. Semi‐hydrogenation of the resulting alkyne 18 to (Z)‐olefin 19 required the use of Pd/C as the catalyst, whereas conventional Lindlar reduction was unsatisfactory. Attempted cis‐dihydroxylation of alkene 22 (formed from 19 by a Mitsunobu reaction with phthalimide) by using catalytic amounts of OsO4 and NMO as the stoichiometric oxidant essentially failed, whereas a stoichiometric osmylation afforded the stable osmate ester 26 a as a single diastereomer. Since the use of OsO4 in stoichiometric amounts deemed inappropriate for a total synthesis project, recourse was taken to catalytic “Blitz dihydroxylation” with RuO4 in the presence of FeCl2⋅4 H2O as co‐catalyst. Application of these conditions to alkene 30 bearing a free aldehyde function at the terminus of the “higher sugar” chain furnished pyranose 32 in good yield and excellent diastereoselectivity, which was converted into the targeted thioglycoside 33 on treatment with PhSSPh/Et3P. It is particularly noteworthy that the conformational constraints of the acyclic substrate 30 enforce the dihydroxylation to violate Kishi's empirical rule for transformations of this type.
Enantioselective Palladium‐Catalyzed Addition of 1,3‐Dicarbonyl Compounds to an Allene Derivative
Authors: Trost Barry M. , Simas Alessandro B. C. , Plietker Bernd , Jäkel Christoph , Xie Jia
Published: September 2005

Enhancing atom economy of the metal‐catalyzed asymmetric allylic alkylation (AAA) shifts from the usual nucleophilic displacement of a leaving group to an addition of a pronucleophile to a double bond. Using 1‐alkoxyallenes as proelectrophiles, the palladium‐catalyzed AAA proceeds with 1,3‐dicarbonyl compounds as pronucleophiles with excellent regioselectivity and enantiomeric excess under optimized conditions. The pH of the medium proved crucial for reactivity/selectivity. By using the more acidic Meldrum's acids, the reactions required a co‐catalytic amount of Brønsted acid, such as trifluoroacetic acid. Single regioisomeric products of 82–99 % ee were obtained. On the other hand, the less acidic 1,3‐diketones failed to react under such conditions. The fact that a less acidic acid like benzoic acid sufficed, suggested the need for general base catalysis as well. Thus, a mixture of triethylamine and benzoic acid proved optimal (ee's 93–99). Employment of the (R,R)‐phenyl Trost ligand gave a product with S configuration. A model to rationalize the results has been developed.
Seismic performance and new design procedure for chevron‐braced frames
Authors: Marino Edoardo M. , Nakashima Masayoshi
Published: September 2005

The paper is concerned with the seismic design of steel‐braced frames in which the braces are configured in a chevron pattern. According to EuroCode 8 (EC8), the behaviour factorq, which allows for the trade‐off between the strength and ductility, is set at 2.5 for chevron‐braced frames, while 6.5 is assigned for most ductile steel moment‐resisting frames. Strength deterioration in post‐buckling regime varies with the brace's slenderness, but EC8 adopts a uniqueqvalue irrespective of the brace slenderness. The study focuses on reevaluation of theqvalue adequate for the seismic design of chevron‐braced frames. The present EC8 method for the calculation of brace strength supplies significantly different elastic stiffnesses and actual strengths for different values of brace slenderness. A new method to estimate the strength of a chevron brace pair is proposed, in which the yield strength (for the brace in tension) and the post‐buckling strength (for the brace in compression) are considered. The new method ensures an identical elastic stiffness and a similar strength regardless of the brace slenderness. The advantage of the proposed method over the conventional EC8 method is demonstrated for the capacity of the proposed method to control the maximum inter‐storey drift. Theqvalues adequate for the chevron‐braced frames are examined in reference to the maximum inter‐storey drifts sustained by most ductile moment‐resisting frames. When the proposed method is employed for strength calculation, theqvalue of 3.5 is found to be reasonable. It is notable that the proposed method does not require larger cross‐sections for the braces compared to the cross‐sections required for the present EC8 method. Copyright © 2005 John Wiley & Sons, Ltd.
A novel predictor–corrector algorithm for sub‐structure pseudo‐dynamic testing
Authors: Ghaboussi J. , Yun G. J. , Hashash Y. M. A.
Published: September 2005

A new predictor–corrector (P–C) method for multi‐site sub‐structure pseudo‐dynamic (PSD) test is proposed. This method is a mixed time integration method in which computational components separable from experimental components are solved by implicit time integration method (Newmark β method). The experiments are performed quasi‐statically based on explicit prediction of displacement. The proposed P–C method has an important advantage as it does not require the determination of the initial stiffness values of experimental components and is thus suitable for representing elastic and inelastic systems. A parameter relating to quality of displacement prediction at boundaries nodes is introduced. This parameter is determined such that P–C method can be applicable to many practical problems. Error‐propagation characteristics of P–C method are also presented. A series of examples including linear and non‐linear soil–foundation–structure interaction problem demonstrate the performance of the proposed method. Copyright © 2005 John Wiley & Sons, Ltd.
An immersed boundary method for incompressible flows using volume of body function
Authors: Pan Dartzi
Published: September 2005

A simple and effective immersed boundary method using volume of body (VOB) function is implemented on unstructured Cartesian meshes. The flow solver is a second‐order accurate implicit pressure‐correction method for the incompressible Navier–Stokes equations. The domain inside the immersed body is viewed as being occupied by the same fluid as outside with a prescribed divergence‐free velocity field. Under this view a fluid–body interface is similar to a fluid–fluid interface encountered in the volume of fluid (VOF) method for the two‐fluid flow problems. The body can thus be identified by the VOB function similar to the VOF function. In fluid–body interface cells the velocity is obtained by a volume‐averaged mixture of body and fluid velocities. The pressure inside the immersed body satisfies the same pressure Poisson equation as outside. To enhance stability and convergence, multigrid methods are developed to solve the difference equations for both pressure and velocity. Various steady and unsteady flows with stationary and moving bodies are computed to validate and to demonstrate the capability of the current method. Copyright © 2005 John Wiley & Sons, Ltd.
Measuring the effects of work loss on productivity with team production
Authors: Nicholson Sean , Pauly Mark V. , Polsky Daniel , Sharda Claire , Szrek Helena , Berger Marc L.
Published: September 2005

Using data from a survey of 800 managers in 12 industries, we find empirical support for the hypothesis that the cost associated with missed work varies across jobs according to the ease with which a manager can find a perfect replacement for the absent worker, the extent to which the worker functions as part of a team, and the time sensitivity of the worker's output. We then estimate wage ‘multipliers’ for 35 different jobs, where the multiplier is defined as the cost to the firm of an absence as a proportion (often greater than one) of the absent worker's daily wage. The median multiplier is 1.28, which supports the view that the cost to the firm of missed work is often greater than the wage. Copyright © 2005 John Wiley & Sons, Ltd.
On the dark rim artifact in dynamic contrast‐enhanced MRI myocardial perfusion studies
Authors: Di Bella E.V.R. , Parker D.L. , Sinusas A.J.
Published: September 2005

A dark band or rim along parts of the subendocardial border of the left ventricle (LV) and the myocardium has been noticed in some dynamic contrast‐enhanced MR perfusion studies. The artifact is thought to be due to susceptibility effects from the gadolinium bolus, motion, or resolution, or a combination of these. Here motionless ex vivo hearts in which the cavity was filled with gadolinium are used to show that dark rim artifacts can be consistent with resolution effects alone. Magn Reson Med, 2005. © 2005 Wiley‐Liss, Inc.
Multitensor approach for analysis and tracking of complex fiber configurations
Authors: Kreher B. W. , Schneider J. F. , Mader I. , Martin E. , Hennig J. , Il'yasov K. A.
Published: September 2005

A multidiffusion‐tensor model (MDT) is presented containing two anisotropic and one isotropic diffusion tensors. This approach has the ability to detect areas of fiber crossings and resolve the direction of crossing fibers. The mean diffusivity and the ratio of the tensor compartments were merged to one independent parameter by fitting MDT to the diffusion‐weighted intensities of a two‐point data acquisition scheme. By an F‐test between the errors of the standard single diffusion tensor and the more complex MDT, fiber crossings were detected and the more accurate model was chosen voxel by voxel. The performance of crossing detection was compared with the spherical harmonics approach in simulations as well as in vivo. Similar results were found in both methods. The MDT model, however, did not only detect crossings but also yielded the single fiber directions. The FACT algorithm and a probabilistic connectivity algorithm were extended to support the MDT model. For example, a mean angular error smaller than 10 degrees was found for the MDT model in a simulated fiber crossing with an SNR of 80. By tracking the corticospinal tract the MDT‐based tracks reached a significantly greater area of the gyrus precentralis. Magn Reson Med, 2005. © 2005 Wiley‐Liss, Inc.
Quantification of cartilage biomechanical and biochemical properties via T1ρ magnetic resonance imaging
Authors: Wheaton Andrew J. , Dodge George R. , Elliott Dawn M. , Nicoll Steven B. , Reddy Ravinder
Published: September 2005

The aim of this study is to develop T1ρ as an MR marker of the compositional and functional condition of cartilage. Specifically, we investigate the correlation of changes in cartilage biomechanical and biochemical properties with T1ρ relaxation rate in a cytokine‐induced model of degeneration. Bovine cartilage explants were cultured with 30 ng/mL of interleukin‐1β to mimic the cartilage degradation of early osteoarthritis. The average rate of T1ρ relaxation was calculated from T1ρ maps acquired on a 4.7 T research scanner. Stress‐relaxation biomechanical tests were conducted with a confined compression apparatus to measure uniaxial aggregate modulus (HA) and hydraulic permeability (k0) using linear biphasic theory. Proteoglycan, collagen, and water content were measured via biochemical assays. Average T1ρ relaxation rate was strongly correlated with proteoglycan content (R2 = 0.926), HA (R2 = 0.828), and log10 k0 (R2 = 0.862). Results of this study demonstrate that T1ρ MRI can detect changes in proteoglycan content and biomechanical properties of cartilage in a physiologically relevant model of cartilage degeneration. The T1ρ technique can potentially be used to noninvasively and quantitatively assess the biochemical and biomechanical characteristics of articular cartilage in humans during the progression of osteoarthritis. Magn Reson Med, 2005. © 2005 Wiley‐Liss, Inc.
CSF cytology has limited value in the evaluation of patients with ependymoma who have MRI evidence of metastasis
Authors: Poltinnikov Igor M. , Merchant Thomas E.
Published: September 2005

Purpose

To investigate the usefulness of cerebrospinal fluid (CSF) cytology in pediatric patients with ependymoma who relapsed after focal irradiation.

Methods

Eighty‐eight patients with ependymoma received conformal radiotherapy (CRT) from July 1997 through January 2003 on an IRB approved prospective treatment protocol. CSF cytology results from evaluations performed prior to CRT and at the time of failure were reviewed for patients who progressed after CRT as documented by magnetic resonance imaging (MRI).

Results

Twenty‐two patients had MRI documented evidence of progression after CRT. Ten patients developed distant failure without local failure, four had combined local and distant failure and eight had local failure without distant failure. The median time from the start of CRT to progression was 19 months (range: 6–73). CSF cytology at diagnosis was negative for the presence of malignant cells in all patients. At the time of progression, CSF cytology was performed in 16 of 22 patients including all 10 patients with distant failure without local recurrence. Malignant cells were not found in any of the evaluated CSF specimens including those with distant failure documented by MRI.

Conclusions

CSF cytology does not add valuable information when evaluating patients with ependymoma who have evidence of distant failure documented by MRI. The usefulness of CSF cytology in the general follow‐up evaluation of pediatric patients with ependymoma remains uncertain. © 2005 Wiley‐Liss, Inc.
Hospital and home chemotherapy for children with leukemia: A randomized cross‐over study
Authors: Stevens Bonnie , Croxford Ruth , McKeever Patricia , Yamada Janet , Booth Marilyn , Daub Stacey , Gafni Amiram , Gammon Janet , Greenberg Mark
Published: September 2005

Background

The study objective was to compare a hospital‐based and a home‐based chemotherapy program for children with acute lymphoblastic leukemia (ALL) in relation to Quality of Life (QOL), safety, caregiver burden, and costs.

Procedure

A randomized cross‐over trial (RCT) design with repeated measures was conducted with 23 children with ALL who attended the oncology outpatient clinic of a metropolitan university affiliated tertiary level pediatric hospital and who also received home visits from a community health services care provider in central Canada.

Results

During the home‐treatment phase, children were more capable of maintaining their usual routines than when receiving hospital chemotherapy (Wilcoxon statistic = 80, P = 0.023), but they appeared to experience greater emotional distress (Wilcoxon sign rank statistic S = 66, P = 0.043) according to parental report. Treatment location had no effect on caregiver burden and adverse effects. No significant differences between groups existed with respect to societal costs of care. As the child's age increased, QOL improved relative to younger children (t20 = −2.37, P = 0.02), the time burden related to child care tasks was reduced (t21 = −3.56, P = 0.002), caregiver effort/difficulty in physical and behavioral support decreased (t21 = −2.09, P = 0.049) and the odds of experiencing one or more adverse events decreased (OR = 0.79, CI = (0.63–1.00), χ = 4.01, P = 0.045).

Conclusions

With few differences noted between groups, these results indicate preliminary support for administrating some or all of a child's chemotherapy at home. Home chemotherapy was associated with specific improvements and decrements in parent reported QOL. No effects were seen on burden of care, adverse events, or cost. Overall, young age adversely affected QOL, burden of care, and adverse events. These data provide important information to families and caregivers as they consider home or hospital‐based therapy in childhood ALL. Pediatr Blood Cancer 2006;47:285–292. © 2005 Wiley‐Liss, Inc.
Mortality rate of adrenocortical tumors in children under 15 years of age in Curitiba, Brazil
Authors: Pianovski Mara A.D. , Maluf Eliane M.C.P. , de Carvalho Denise S. , Ribeiro Raul C. , Rodriguez‐Galindo Carlos , Boffetta Paolo , Zancanella Patrícia , Figueiredo Bonald C.
Published: September 2005

Background

Several reports refer to an increased frequency of adrenal cortex tumors (ACT) among children in Southern Brazil, yet all data have been derived from hospital‐based registries. An inherited germline mutation in the p53 gene (TP53 R337H) is detected in virtually all children with ACT in this region and accounts for the excess cases observed.

Procedure

We reviewed all death certificates that mentioned ACT or adrenal neuroblastoma (NB) and which were reported to the Paraná State Department of Health between 1998 and 2003, for individuals younger than 15 years who resided in the Curitiba metropolitan region.

Results

Eight deaths from ACT and ten from NB were identified. The age‐standardized mortality rate per million children <15 years of age in the Curitiba metropolitan region during the years 1998–2003 was 1.6 (95% confidence interval (CI) 1.4, 1.8) for ACT and 2.3 (95% CI 2.0, 2.5) for NB. The ratio of the adrenal NB and ACT age‐adjusted mortality rates was 1.43. The incidence of ACT estimated from the mortality data, assuming an ACT survival rate of 0.542, was 3.5 (95% CI 2.9, 4.2).

Conclusions

Our investigation of population‐based mortality confirms the evidence from hospital‐based registries of a clustering of ACT in Southern Brazil. In addition, our data suggest that the incidence of ACT in this region is about 12–18 times the incidence reported in the United States and Europe. © 2005 Wiley‐Liss, Inc.
T cell epitope definition by differential mass spectrometry: Identification of a novel, immunogenic HLA‐B8 ligand directly from renal cancer tissue
Authors: Flad Thomas , Mueller Ludmila , Dihazi Hassan , Grigorova Veneta , Bogumil Ralf , Beck Alexander , Thedieck Cornelia , Mueller Gerhard A. , Kalbacher Hubert , Mueller Claudia A.
Published: September 2005

In this study, we describe a differential mass spectrometric technique for the immuno‐proteomic analysis of the major histocompatibility complex (MHC) peptides of a renal cell carcinoma (RCC) biopsy compared with the healthy kidney tissue of the same patient after nephrectomy. Using a stable isotope labeling approach, we could directly compare and relatively quantify 43 MHC‐peptide pairs, most of which were present in similar proportions on both normal kidney and tumor. Significantly, two dominant peptides of monoisotopic masses ([M+H]+) 973.43 u and 967.59 u, respectively, were found exclusively in the tumor sample. One of these was identified as originating from heme oxygenase‐1 (HO‐1), a protein involved in induction of apoptosis resistance, immuno‐suppression and neoangiogenesis and reported to be up‐regulated in various cancer types. Moreover, the corresponding synthetic HO‐1‐derived peptide was shown to be immunogenic in vitro by generation of CD8+ T cell lines with peptide‐specific cytolytic activity. Thus, this peptide is an example of a differentially identified T cell epitope that could be considered as a target for immunotherapy.
(Co)polymerization behavior of supported metallocene catalysts. I. Ligand and substituent effect
Authors: Białek Marzena , Czaja Krystyna , Reszka Aleksandra
Published: September 2005

Ethylene polymerization and its copolymerization with 1‐hexene with a set of supported metallocene catalysts were studied. As a carrier, the complex of magnesium chloride with tetrahydrofuran, which was previously pretreated with a triisobutylaluminium (TIBA), was used. The investigated metallocene compound differs in the metal type (Zr or Ti), the nature of the alkyl substituent in the cyclopentadienyl ring, and the type of ligand (Cp or Ind). The effect of catalyst composition on the anchored metal content, catalyst activity, comonomer reactivity, and polymer properties was investigated. The results obtained with supported catalysts were compared with those obtained with their homogeneous counterparts under the same (co)polymerization conditions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5562–5570, 2005
Poly(ionic liquid)s as new materials for CO2 absorption
Authors: Tang Jianbin , Tang Huadong , Sun Weilin , Radosz Maciej , Shen Youqing
Published: September 2005

A series of imidazolium‐based ionic liquid monomers and their corresponding polymers (poly(ionic liquid)s) were synthesized, and their CO2 sorption was studied. The poly(ionic liquid)s had enhanced CO2 sorption capacities and fast sorption/desorption rates compared with room temperature ionic liquids. The effects of the chemical structures, including the types of anion, cation, and backbone of the poly(ionic liquid)s on their CO2 sorption have been discussed. In contrast to room temperature ionic liquids, the polymer with PF anions had the highest CO2‐sorption capacity, while those with BF or Tf2N− anions had the same capacities. The CO2 sorption and desorption of the polymers were fast and reversible, and the sorption was selective over H2, N2, and O2. The measured Henry's constants of P[VBBI][BF4] and P[MABI][BF4] were 26.0 bar and 37.7 bar, which were lower than those of similar room temperature ionic liquids. The preliminary study of the mechanism indicated that the CO2 sorption of the polymer particles was more absorption (the bulk) but less adsorption (the surface). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5477–5489, 2005
Synthesis and self‐assembly of hyperbranched polymers with benzoyl terminal arms
Authors: Jiang Guohua , Wang Li , Chen Tao , Dong Xiaochen , Yu Haojie , Wang Jianfeng , Chen Chang
Published: September 2005

Hyperbranched polyesters (HPs) with a variable content of benzoyl terminal groups were synthesized through the chemical modification of the HPs' cores by substituting a controlled fraction of the terminal hydroxyl groups with benzoyl chloride. The resulting hyperbranched polymers that were modified by benzoyl groups (HPs‐B) were characterized by 1H NMR, FTIR, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). Research results revealed that self‐assembled structures could be formed in selected solvents (acetone/n‐hexane). It was found that the morphologies of self‐assembled structures could be adjusted by controlling the content of outside benzoyl terminal groups in the hyperbranched polymers, the volume ratio of acetone with n‐hexane, and the concentration of the hyperbranched polymers with benzoyl terminal arms. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5554–5561, 2005
Metallocene supported on a polyhedral oligomeric silsesquioxane‐modified silica with high catalytic activity for ethylene polymerization
Authors: Bianchini Daniela , Galland Griselda Barrera , dos Santos João Henrique Z. , Williams Roberto J. J. , Fasce Diana P. , Dell'Erba Ignacio E. , Quijada Raul , Perez Mónica
Published: September 2005

A polyhedral oligomeric silsesquioxane (POSS) consisting of a mixture of perfect and imperfect polyhedra with 8–10 Si atoms bonded to bulky and branched organic groups functionalized with (β‐hydroxy)‐tertiary amines, was adsorbed on an activated silica from a toluene solution. POSS fixation was confirmed by measuring its concentration in the solutions resulting from filtering and repeatedly washing with toluene. Diffuse reflectance infrared Fourier‐transformed (DRIFTS) spectra of the modified silica showed a decrease in the absorption of isolated SiOH groups. A POSS previously marked by reaction with an isocyanate was also used, and the presence of the carbonyl in the urethane group was recorded in the DRIFTS spectra of the modified silica, confirming the presence of adsorbed POSS. X‐ray photoelectron spectroscopy (XPS) was used to measure the amount of Si (2p) of POSS adsorbed on the SiO2 surface as a function of the POSS concentration in the toluene solution. A linear increase of adsorbed POSS as a function of its concentration in toluene was found, even after successive washings with toluene. A metallocene, (nBuCp)2ZrCl2, was then adsorbed on the POSS‐modified silica from a toluene solution, and the fixed Zr amount was measured by Rutherford backscattering spectrometry (RBS). The activity of the resulting catalyst for ethylene polymerization in toluene, using methylaluminoxane (MAO) as a cocatalyst, was determined in two different devices operating in the range of 1.6–7.0 bar. Under every experimental condition, POSS‐modification of the silica support led to an increase of about 50% in the activity of the resulting catalyst when compared to the use of the unmodified support. Reasons for the observed increase in activity are discussed. The molar mass distribution and crystallinity of the resulting polyethylenes was not affected by the POSS modification of the silica support. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5465–5476, 2005
Self‐efficacy, coping, and difficulties interacting with health care professionals among women living with breast cancer in rural communities
Authors: Collie K. , Wong P. , Tilston J. , Butler L. D. , Turner‐Cobb J. , Kreshka M. A. , Parsons R. , Graddy K. , Cheasty J. D. , Koopman C.
Published: September 2005

This study examined self‐efficacy, coping, and social support in relation to difficulties interacting with physicians and nurses among women living with breast cancer. One hundred women living in rural, mountainous communities of northeastern California were recruited, with 89 providing complete data for this study. All women completed a battery of questionnaires that included the CARES—Medical Interaction Subscale and measures of self‐efficacy, coping, satisfaction with social support, and demographic and medical characteristics. In a multiple regression analysis, difficulties interacting with medical professionals were found to be greater among women who were not married, who used more behavioral disengagement or less self‐distraction to cope with breast cancer, and who reported less self‐efficacy for affect regulation and for seeking and understanding medical information. Emotional venting and satisfaction with social support for dealing with cancer‐related stress were not, however, significantly related to difficulties in interacting with the medical team. This model accounted for an adjusted value of 42% of the variance. Further research is needed to identify possible causal relationships related to these findings and to determine what interventions might be warranted to improve medical interactions for women with breast cancer living in rural areas. Copyright © 2005 John Wiley & Sons, Ltd.
‘Being known’: patients' perspectives of the dynamics of human connection in cancer care
Authors: Thorne Sally E. , Kuo Margot , Armstrong Elizabeth‐Anne , McPherson Gladys , Harris Susan R. , Hislop T. Gregory
Published: September 2005

In the context of a large study of effective and ineffective cancer care communications from the perspective of patients with cancer, the authors documented the pervasiveness of the desire for human connection. Analyzing accounts from 200 patients with diverse cancer experiences, they concluded that, while anonymity is generally antithetical to a comfortable cancer care encounter, there are wide variations in what it means to ‘be known’ in a meaningful way. In this discussion, a description of the dynamics of being known and not being known within the cancer care encounter is presented, and a range of variations considered. By illuminating the manner in which communication influences human connection within the cancer care context, the findings of this study challenge some current research directions and propose alternative conceptualizations that might better orient future inquiry to enhance practice. Copyright © 2005 John Wiley & Sons, Ltd.
Developing communication competency in the context of cancer: a critical interpretive analysis of provider training programs
Authors: Butler Lorna , Degner Lesley , Baile Walter , Landry M.
Published: September 2005

We conducted a critical interpretive analysis of 47 studies from the Cochrane Review of the communications training literature to capture the empirical indicators used to judge provider communication competency and to describe how the indicators were characterized in the context of a cancer care system. Of the 47 studies reviewed, few showed any resemblance to recommendations from two international consensus conferences of experts in the communication research field. Some of the challenges in moving forward with cancer‐related communication skills involve deciding what we want people to learn, providing learning across various experiences, identifying learning models, and finding alternate ways of motivating people to learn. Once core competencies are clearly articulated, we can determine the best approaches for developing cancer‐specific training programs. Copyright © 2005 John Wiley & Sons, Ltd.
The communication goals and needs of cancer patients: a review
Authors: Hack Thomas F. , Degner Lesley F. , Parker Patricia A.
Published: September 2005

The aim of this review paper is to critique the empirical literature pertaining to the communication needs and goals of cancer patients, and to provide direction for research in this area. According to the conceptual framework of Feldman‐Stewart et al., patient–physician communication occurs for the fundamental purpose of addressing each participant's goal(s). This review is divided into two categories of goals: (a) optimal medical management of the cancer, and (b) optimal attention to the patient's psychosocial response to cancer. Optimal medical management includes discussions about disease status and the treatment plan, and the effectiveness of these discussions is frequently determined by assessing patient understanding, satisfaction, and well‐being. The literature suggests that cancer patients continue to have unmet communication needs, and communication outcomes are enhanced when physicians attend to the emotional needs of patients. Research gaps in communication research are highlighted, including the need for additional study of several external factors affecting the patient and provider. Copyright © 2005 John Wiley & Sons, Ltd.
A conceptual framework for patient–professional communication: an application to the cancer context
Authors: Feldman‐Stewart D. , Brundage M.D. , Tishelman C.
Published: September 2005

We present a conceptual framework of one‐to‐one, in‐person communication that occurs between a health‐care professional and a patient. The framework is intended as a tool for organizing and summarizing relevant research but it can also help guide assessing the communication process and can help guide development of interventions to improve the process.

The framework includes four key components, with a focus on elements that can be modified. The first component is the focus of the interaction: each participant's communication goals. The second component consists of the participants themselves, each with five key attributes that determine, in part, how they address their goals. The third component is the communication process: each person both conveys messages and receives messages, and the messages themselves can be verbal, non‐verbal, or silent. The communication process is iterative and extended in time with one act having an impact on following acts. Finally, the fourth component is the environment in which the communication occurs, both the immediate physical setting and the context beyond. Important aspects of the environment, identified as external factors, affect the communication process through their impact on the participants' attributes.

The framework builds on classic communication frameworks to which it adds unique elements. Some of its unique aspects include the prominent role of the participants' goals and its distinct recognition that messages are conveyed through silence. The framework serves as a common conceptualization of factors important to successful communication for the remaining review papers in this series and for future studies of practitioner–patient communication. Copyright © 2005 John Wiley & Sons, Ltd.
Patient–professional communication research in cancer: an integrative review of research methods in the context of a conceptual framework
Authors: Carlson Linda E. , Feldman‐Stewart Deb , Tishelman Carol , Brundage Michael D.
Published: September 2005

This paper uses the conceptual framework of Feldman‐Stewartet al. to organize and review the types of research methodologies used to investigate various aspects of patient‐health care professional communication in the context of cancer. Research methods employed are classified as either non‐experimental or experimental. Non‐experimental designs include naturalistic observational studies (e.g. participant observation, audio‐ or videotaping of interactions) and retrospective introspective descriptions (e.g. self‐report questionnaires, qualitative interview methods). Experimental designs often involve interventions aimed at improving communication, such as physician or patient training, and the use of technology to enhance communication (e.g. audiotapes, computers).

Using the conceptualization of the communication framework description, we argue that the outcome measures used in these studies address either primary goals, enabling goals, or secondary communication outcomes. Outcomes that are related to primary goals of the communication exchange include assessing the level of understanding of information conveyed, aspects of decision making, planning around treatments, or general provision of care. Outcomes related to enabling goals focus on elements that affect the ability to achieve primary goals. Outcomes secondary to the communication do not relate directly to what the communication is attempting to achieve. We conclude by identifying priority areas for further research, such as identifying the goals of both participants, understanding how particular aspects of the communication process affect their ability to achieve their goals, and examining the external environment in which communication takes place. Copyright © 2005 John Wiley & Sons, Ltd.
The toxicity of herbicides to non‐target aquatic plants and algae: assessment of predictive factors and hazard
Authors: Cedergreen Nina , Streibig Jens C
Published: September 2005

Widely used herbicides sometimes inadvertently contaminate surface waters. In this study we evaluate the toxicity of herbicides to aquatic plants and algae and relate it to environmental herbicide concentrations and exposure scenarios, herbicide formulation and mode of action. This was done experimentally for ten herbicides, using the aquatic macrophyte Lemna minor L. and the green alga Pseudokirchneriella subcapitata (Korshikov) Hindak, supplemented with a database study comprising algae toxicity data for 146 herbicides. The laboratory study showed that herbicide formulations in general did not enhance herbicide efficacy in the aquatic environment. The Roundup formulation of glyphosate proved to be the only exception, decreasing the EC50 of the technical product for both L. minor and P. subcapitata approximately fourfold. Comparison of the sensitivity of L. minor and P. subcapitata revealed up to 1000‐fold higher sensitivity of L. minor for the herbicides categorized as weak acids (pKa < 5), emphasizing the importance of higher plants in hazard assessment. Database analyses showed that no herbicide group, categorized by site of action, was significantly more toxic than another. Synthetic auxins were the exception as they are virtually non‐toxic to unicellular algae. There was no strong correlation between toxicity to algae and Kow of the herbicides, not even within groups having the same site of action. Evaluating all data, few herbicides were toxic at concentrations below 1 µg litre−1, which is the 99.9th percentile of the herbicide concentrations measured in the Danish surveillance programme. Joint action of several herbicides cannot however be excluded. Copyright © 2005 Society of Chemical Industry
Ion‐assisted nanorod growth by dc magnetron sputtering
Authors: Rogov A. V. , Fanchenko S. S. , Varfolomeev A. E.
Published: September 2005

High‐rate cathode growth of nanorods is observed for dc magnetron sputtering of graphite, germanium and molybdenum cathodes despite the sputtering. The growth of vertically aligned carbon nanorods using dc magnetron sputtering with deuterium as the working gas and a polycrystalline nuclear graphite cathode is reported for the first time. Two different types of carbon nanorodes are observed differing in their diameter/length ratio. High‐rate nanorod growth is also observed for the usual magnetron sputtering with argon as a working gas for molybdenum and germanium single‐crystal cathodes. The high growth rate (tens of micrometres per hour) is discussed in the context of ion‐stimulated surface mobility of the neutral atoms and their redeposition in nonhomogeneous cathode sputtering. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Characteristics of single‐crystal AlN films grown on ferromagnetic metal substrates
Authors: Okamoto K. , Inoue S. , Matsuki N. , Kim T.‐W. , Fujioka H. , Oshima M.
Published: September 2005

We have demonstrated the first single‐crystal growth of AlN films on Fe substrates using pulsed laser deposition and in‐vestigated their structural properties. Stepped and terraced surfaces of the Fe(110) substrates have been achieved by UHV annealing. Although a low quality AlN film, with ran‐domly oriented polycrystalline grains, grows at a substrate temperature of 510 °C, a single‐crystal AlN film is achieved by lowering the growth temperature down to 430 °C. The dis‐tributions of crystal orientations in the tilt and the twist direc‐ tions for a AlN film measured by electron backscattered diffraction (EBSD) are 0.26º and 0.58º, respectively. Neither 30º rotational domains nor cubic phase domains exist in the AlN films. We have also found that the intermixing reactions between AlN and the Fe substrates are fully suppressed and the heterointerface is atomically abrupt. These results indicate that low temperature PLD growth technique allows us to grow single‐crystal AlN on ferromagnetic substrates with an atomically abrupt interface. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Predictive Genetic Testing for Hereditary Breast and Ovarian Cancer: Psychological Distress and Illness Representations 1 Year Following Disclosure
Authors: Claes E , Evers‐Kiebooms G. , Denayer L. , Decruyenaere M. , Boogaerts A. , Philippe K. , Legius E.
Published: September 2005

This prospective study evaluates emotional functioning and illness representations in 68 unaffected women (34 carriers/34 noncarriers) 1 year after predictive testing for BRCA1/2 mutations when offered within a multidisciplinary approach. Carriers had higher subjective risk perception of breast cancer than noncarriers. Carriers who did not have prophylactic oophorectomy had the highest risk perception of ovarian cancer. No differences were found between carriers and noncarriers regarding perceived seriousness and perceived control of breast and ovarian cancer. Mean levels of distress were within normal ranges. Only few women showed an overall pattern of clinically elevated distress. Cancer‐specific distress and state‐anxiety significantly decreased in noncarriers from pre‐ to posttest while general distress remained about the same. There were no significant changes in distress in the group of carriers except for ovarian cancer distress which significantly decreased from pre‐ to posttest. Our study did not reveal adverse effects of predictive testing when offered in the context of a multidisciplinary approach.
Who Are the Next Generation of Genetic Counselors? A Survey of Students
Authors: Lega Melanie , Veach Patricia McCarthy , Ward Erin E. , LeRoy Bonnie S.
Published: September 2005

Genetic counseling students were surveyed about their backgrounds, application process to genetic counseling programs, and career motivations and plans. Program directors from 27 accredited programs were asked to distribute 362 surveys to students. Fifty‐two survey items assess demographics; sources of support for pursuing a genetic counseling career (information about genetic counseling, encouragement/discouragement from others); career motivations (reasons for applying and for becoming a genetic counselor); and career certainty. Two hundred and thirty‐five usable surveys were returned (64.9% usable return rate). Most respondents were Caucasian females (mean age = 25.4 years). About 13% identified as ethnic minorities, and about one‐third reported family histories of a genetic condition(s). Most respondents learned about the field in classes, and most were strongly encouraged by family and friends to pursue genetic counseling. Reasons rated as most important for becoming a genetic counselor included helping others and intellectual stimulation. Recruitment, training, and research recommendations are given.
Development and validation of the Basic Empathy Scale
Authors: Jolliffe Darrick , Farrington David P.
Published: September 2005

In developing the Basic Empathy Scale (BES), 40 items measuring affective and cognitive empathy were administered to 363 adolescents in Year 10 (aged about 15). Factor analysis reduced this to a 20‐item scale that was administered 1 year later to 357 different adolescents in Year 10 in the same schools. Confirmatory factor analysis verified the two‐factor solution. Females scored higher than males on both affective and cognitive empathy. Empathy was positively correlated with intelligence (for females only), extraversion (cognitive empathy only) neuroticism (affective empathy only), agreeableness, conscientiousness (for males only), and openness. Empathy was positively related to parental supervision and socioeconomic status. Adolescents who would help victims of bullying had high empathy.
Non‐invasive measurement of cardiac output by whole‐body bio‐impedance during dobutamine stress echocardiography: Clinical implications in patients with left ventricular dysfunction and ischaemia
Authors: Leitman Marina , Sucher Edgar , Kaluski Edo , Wolf Ruth , Peleg Eli , Moshkovitz Yaron , Milo‐Cotter Olga , Vered Zvi , Cotter Gad
Published: September 2005

Objectives:

To compare non‐invasive determination of cardiac index (CI) by whole body electrical bioimpedance using the NICaS apparatus and Doppler echocardiography, and the role of cardiac power index (Cpi) and total peripheral resistance index (TPRi) calculation during dobutamine stress echocardiography (DSE).

Subjects and methods:

We enrolled 60 consecutive patients undergoing DSE. Patients were prospectively divided into 3 groups: Group 1 (n=20): normal DSE (control). Group 2 (n=20): EF<40% without significant ischaemia. Group 3 (n=20): patients with significant ischaemia on DSE. Measurements of CI were performed at the end of each stage of DSE by both echocardiographic left ventricular outflow track flow and the NICaS apparatus, using whole‐body bio‐impedance. MAP was measured simultaneously and TPRi and Cpi were calculated.

Results:

The correlation between non‐invasive CI as determined by NICaS and echocardiography was 0.81, although Echocardiographic readings of CI were higher during administration of higher doses of dobutamine. Lower EF correlated with lower Cpi, especially stress induced Cpi. Hence, patients with reduced EF (group 2) had a blunted increase in Cpi during stress. Patients with ischaemia (group 3) had a blunted increase in Cpi as well as a decrease in Cpi and increase in TPRi during the last stages of DSE.

Conclusion:

Measurement of CI by NICaS correlated well with Doppler derived CI. The calculation of Cpi and TPRi changes during dobutamine stress may provide important clinical information.