bluuebunny/crossref_metadata_2025 huggingface dataset:
Repeat Exposure to Incremental Doses of Acetaminophen Provides Protection Against Acetaminophen–Induced Lethality in Mice: An Explanation for High Acetaminophen Dosage in Humans Without Hepatic Injury
Authors: Shayiq Rass M. , Roberts Dean W. , Rothstein Kenneth , Snawder John E. , Benson Wayne , Ma Xiang , Black Martin
Published: July 2004

In studies designed to simulate a clinical observation in which an individual became tolerant to normally lethal doses of acetaminophen (APAP), mice were pretreated with increasing doses of APAP for 8 days and challenged on day 9 with normally supralethal doses of APAP. These animals developed minimal hepatotoxicity after a challenge dose with a fourfold increase in LD50 to 1,350 mg/kg. The pretreatment regimen resulted in hepatic changes including: centrilobular localization of 3–(cysteine–S–yl)APAP protein adducts, selective down–regulation of cytochrome P4502E1 (CYP2E1) and CYP1A2 that produced the toxic metabolite, N–acetyl–p–benzoquinone imine, higher levels of reduced glutathione (GSH), centrilobular inflammation, and a fourfold increase in hepatocellular proliferation. The protection against the lethal APAP doses afforded by pretreatment is secondary to these changes and to the associated regional shift in the bioactivation of the APAP challenge dose from centrilobular to periportal regions where CYP2E1 is not found, protective GSH is more abundant, and where cell–proliferative responses are better able to sustain repair. This shift in APAP bioactivation results in less–intense covalent binding that is more diffuse and spread uniformly throughout the hepatic lobe, most likely contributing to protection by delaying the early onset of liver injury that has been generally associated with centrilobular localization of the adducts. Intervention of APAP pretreatment-induced cell division in mice with colchicine left them resistant to a 500–mg/kg (normally lethal) dose of APAP, but unable to survive a 1,000–mg/kg APAP challenge dose. The data demonstrate multiple mechanistic components to the protection afforded by APAP pretreatment. Whereas metabolic and physiological changes not dependent on cell proliferation are adequate to protect against 500 mg/kg APAP, these changes plus a potentiated cell–proliferative response are necessary for protection against the supralethal 1,000–mg/kg APAP dose. Furthermore, the data document an uncoupling of the traditional association between covalent binding and toxicity, and suggest that the assessment of toxicity following repeated or chronic APAP exposure must consider altered drug interactions and parameters besides those historically used to assess acute APAP overdose.

(Hepatology 1999;29:451–463.)
Ccaat/Enhancer Binding Protein α (C/Ebpα) Is An Important Mediator of Mouse C/Ebpβ Protein Isoform Production
Authors: Burgess-Beusse Bonnie L. , Timchenko Nikolai A. , Darlington Gretchen J.
Published: July 2004

Both CCAAT/enhancer binding protein α (C/EBPα) and C/EBPβ are intronless, yet can create various N–terminally truncated protein products with distinct DNA binding and transactivation potentials. These proteins can be generated via two distinct mechanisms, one translational and the other post–translational. In the translational mechanism, there is alternative translational start site selection of the different AUG codons present in the single messenger RNA (mRNA) species via a process of leaky ribosome scanning. Additionally, a post–translational method of isoform formation, through specific proteolytic cleavage of the full length protein has also been described. In this manuscript, we present evidence that the production of C/EBPβ protein isoforms in the neonatal mouse liver is regulated by C/EBPα. In C/EBPα knockout mice, the predominant C/EBPβ proteins are the larger 38– and 35–kd isoforms, whereas wild–type animals primarily possess the smaller 21– and 14–kd isoforms. These C/EBPα–dependent differences are liver specific, not present in lung or adipose tissues, and present at day 18 of development. Additionally, we show that induction of C/EBPα expression leads to an increase in the production of the 21–kd C/EBPβ isoform in cell culture studies. As the various C/EBPβ protein isoforms have different transcriptional capabilities, it is important to understand the regulation of the production of these isoforms. Our observations suggest a novel role for the C/EBPα transcription factor in this process.
Intramolecular Asymmetric Amidations of Sulfonamides and Sulfamates Catalyzed by Chiral Dirhodium(II) Complexes
Authors: Fruit Corinne , Müller Paul
Published: July 2004

Enantioselective intramolecular amidation of aliphatic sulfonamides was achieved for the first time by means of chiral carboxylatodirhodium(II) catalysts in conjunction with PhI(OAc)2 and MgO in high yields and with enantioselectivities of up to 66% (Scheme 3, Table 1). The best results were obtained with [Rh2{(S)‐nttl)4] and [Rh2{(R)‐ntv)4] as catalysts ((S)‐nttl=(αS)‐α‐(tert‐butyl)‐1,3‐dioxo‐2H‐benz[de]isoquinoline‐2‐acetato, (R)‐nto=(αR)‐α‐isopropyl‐1,3‐dioxo‐2H‐benz[de] isoquinoline‐2‐acetato). In addition, these carboxylatodirhodium(II) catalysts were also efficient in intramolecular amidations of aliphatic sulfamates esters, although the enantioselectivity of these latter reactions was significantly lower (Scheme 4, Table 3).
Unsymmetrical Unsaturated Ketones from Lactones and Carboxylic Acids in One Step
Authors: Giersch Wolfgang , Naef Ferdinand
Published: July 2004

A one‐step transformation of γ‐ and δ‐(spiro)lactones into γ,δ‐ and δ,ε‐unsaturated ketones in the presence of carboxylic acids in the vapor phase at 400° over a supported manganese catalyst is reported for the first time. The scope of this new transformation is exemplified with a series of lactones, and a mechanistic rationale is proposed.
Internal Nucleophilic Termination in Acid‐Mediated Polyene Cyclizations. Part 3
Authors: Snowden Roger L. , Eichenberger Jean‐Claude , Linder Simon , Sonnay Philippe
Published: July 2004

Treatment of the unsaturated allenic alcohols (E)‐7, (Z)‐7, 10, 13, and 19 with an excess of FSO3H in 2‐nitropropane at −90° to −30° afforded, in 68–85% yield, diastereoisomer mixtures of racemic tricyclic ethers 14a–d and 20a–d, respectively (Schemes 3 and 5), with high stereoselectivity (see Table and Scheme 6). These stereospecific transformations represent the first reported examples of an acid‐mediated polyene cyclization, in which an alkene is the initiating group and an allenic alcohol serves as the internal terminator. In close analogy to our earlier work, a nonsynchronous process is postulated, whereby the stereochemical course of cyclization is directed by the conformational structure of an intermediate cyclohexyl cation (see Schemes 3 and 6). In addition, the organoleptic properties of 14c and 20c, racemic didehydro and methyl didehydro analogues, respectively, of the known odorant Ambrox® ((−)‐4f), are briefly discussed.
Asymmetric Reaction of Simple Nitro Compounds with Chiral 1,3‐Oxazolidin‐2‐ones
Authors: Kudyba Iwona , Raczko Jerzy , Jurczak Janusz
Published: July 2004

The chiral oxazolidinone 1 (=[(3aS,6R,7aR)‐tetrahydro‐8,8‐dimethyl‐2‐oxo‐4H‐3a,6‐methano‐1,3‐benzoxazol‐3‐yl](oxo)acetaldehyde) was found to react stereoselectively with simple nitro compounds in the presence of Al2O3 or Bu4NF⋅3 H2O (TBAF) as catalysts, affording the diastereoisomeric nitro alcohols 3–6 with good asymmetric induction. When Al2O3 was used, the (S)‐configuration at the center bearing the OH group was generated, with the relative syn‐configuration for the major diastereoisomers. In the case of the nitro‐aldol reaction catalyzed by TBAF, an opposite asymmetric induction was found for two nitro compounds. In contrast to 1, compound 12 (=((4R,5S)‐4‐methyl‐2‐oxo‐5‐phenyl‐1,3‐oxazolidin‐3‐yl)(oxo)acetaldehyde), a derivative of Evans auxiliary, gave rise to poor asymmetric induction in Henry reactions.
Synthesis and Properties of Conformationally Constrained Analogues of Floral‐Type Odorants
Authors: Lamboley Serge , Morel Cédric , de Saint Laumer Jean‐Yves , Boschung André F. , Richards Nigel G. J. , Winter Béat M.
Published: July 2004

The twelve bridged analogues 8–19 of floral‐type odorants related to cyclamenaldehyde (1) were synthesized (Schemes 1–5) to investigate the relationship between the structural and conformational features of these compounds and their odor properties. Comparison of the data from sensory evaluation and molecular modeling suggests that the side chain of both the unconstrained and the constrained active analogues is not extended (anti) but rather folded (gauche) in the ‘bioactive’ conformation. However, it is mainly the nature of the substituents at the α position of the aldehyde function that critically influences the odor quality and strength. These studies provide new information that should aid ongoing efforts to develop models of odorantreceptor interactions.
Studies on the Synthesis of Di‐ and Trisaccharide Analogues of Moenomycin A. Modifications in Unit E and in the Lipid Part
Authors: Yang Guangbin , Mansourova Madina , Hennig Lothar , Findeisen Matthias , Oehme Ramona , Giesa Sabine , Welzel Peter
Published: July 2004

Routes allowing the synthesis of moenomycin analogues with one modified sugar component and with new lipid parts were developed (see 10c, 12c, 16b, and 20b in Schemes 2–4). It is anticipated that such analogues will be useful for studying the mode of action of the moenomycin‐type transglycosylase inhibitors in detail and for preparing analogues with improved pharmacokinetic properties.
Syntheses and Odor Descriptions of Cyclopropanated Compounds. Part 5
Authors: Kiyota Hiromasa , Takigawa Shin‐ya , Kuwahara Shigefumi
Published: July 2004

Analogs of methyl jasmonate (=methyl (1R*,2R*)‐3‐oxo‐2‐[(Z)‐pent‐2‐enyl]cyclopentaneacetate; MJA) bearing a cyclopropane ring, double bond, or a F‐substituent were synthesized, and their odor characteristics were examined. Most of the analogs with the same stereochemical properties as methyl epijasmonate showed odor properties superior to MJA. Interestingly, the enol acetate of MJA had a diffusive orchid‐like note.
Synthesis of 4‐(Phenylamino)quinazoline‐2(1H)‐selones and Diselenides from Isoselenocyanates: Dimroth Rearrangement of an Intermediate
Authors: Atanassov Plamen K. , Linden Anthony , Heimgartner Heinz
Published: July 2004

The reaction of anthranilonitriles 8 with phenyl isoselenocyanates (1a) in dry pyridine under reflux gave 4‐(phenylamino)quinazoline‐2(1H)‐selones 9 (Scheme 2). They are easily oxidized and converted to diselenides of type 11. The analogous reaction of 8a with phenyl isothiocyanate (1b) yielded the quinazoline‐2(1H)‐thione 10 (Scheme 2). A reaction mechanism via a Dimroth rearrangement of the primarily formed intermediate is presented in Scheme 3. The molecular structures of 10 and 11a have been established by X‐ray crystallography. Unexpectedly, no selone or diselenide was obtained in the case of the reaction with 3‐aminobenzo[b]furan‐2‐carbonitrile (14). The only product isolated was the selenide 16 (Scheme 4), the structure of which has been established by X‐ray crystallography.
Photochemistry of Spiro[6H‐[1,3]Oxathiin‐2,2′‐tricyclo[3.3.1.13,7]decan]‐ 6‐one
Authors: Schmidt Kerstin , Margaretha Paul
Published: July 2004

On irradiation (300 nm) in the solid state, the title compound 8 affords tricyclo[3.3.1.13,7]decan‐2‐one (=adamantan‐2‐one; 9) selectively via [4+2] cycloreversion. A similar result is obtained on photolysis in solution (MeCN or acetone), also in the presence of added alkenes. On irradiation in MeOH, a solvent adduct 11 is isolated in addition to 9. From experiments in CD3OD, it can be inferred that 11 is formed via syn‐addition of MeOH to the ground‐state (E)‐heterocycle 16.
Encapsulating chondrocytes in copolymer gels: Bimodal degradation kinetics influence cell phenotype and extracellular matrix development
Authors: Rice Mark A. , Anseth Kristi S.
Published: July 2004

Hydrogels provide an ideal environment for encapsulating chondrocytes and facilitating the production of cartilaginous tissue. However, the deposition of extracellular matrix (ECM) and ultimate tissue function are significantly affected by degradation of gel scaffolds. It was hypothesized that a bimodal degradation process would capture the critical features necessary for neotissue development. Specifically, most of the initial crosslinks would degrade quickly and enable ECM deposition, whereas a critical amount would remain or degrade much more slowly to provide structural integrity over a longer time period. In this study, chondrocytes were encapsulated in copolymer gels of nondegradable [poly(ethylene glycol) dimethacrylate] and degradable [poly(lactic acid)‐b‐poly(ethylene glycol)‐b‐poly(lactic acid) dimethacrylate] macromers to investigate the effects of gel degradation on ECM evolution. All gels were synthesized from 10 wt % total macromer solutions consisting of 0, 19, 21, 23, 25, or 100 mol % nondegradable units. The copolymer constructs were found to have lower DNA content than completely degradable constructs after 8 weeks. However, total biochemical content was very similar among the various copolymer constructs. Histological analysis gave more interesting insight, showing a more uniform spatial distribution of ECM components in copolymer samples than in constructs with 100 mol % nondegradable units. In addition, a number of major structural defects were present in constructs with 0 mol % nondegradable units that became less apparent as the amount of nondegradable units was increased. Overall, the copolymer gels had a higher compressive modulus during neotissue development and also showed no evidence of chondrocyte dedifferentiation. With their bimodal degradation profile, copolymer gels with carefully selected ratios of degrading to slow or nondegrading crosslinks provide distinct advantages for ECM development in tissue‐engineered cartilage. © 2004 Wiley Periodicals, Inc. J Biomed Mater Res 70A: 560–568, 2004
Cover Picture: Macromol. Chem. Phys. 11/2004
Authors: Safronov Alexander P. , Smirnova Yelena A. , Pollack Gerald H. , Blyakhman Felix A.
Published: July 2004

Cover: Partly dehydrated gels of potassium poly(acrylate) change their enthalpy as referred to maximum swollen equilibrium gel, due to the changes in molecular and ionic interactions. Microcalorimetry measurements of swelling to equilibrium for such gels reveal an enthalpy “spectrum”, which makes it possible to evaluate separately main contributions to molecular interactions in polyelectrolytes.

Further details can be found in the Full Paper by A. P. Safronov,* Y. A. Smirnova, G. H. Pollack, and F. A. Blyakhman on page 1431.
Hydrodynamic Effect on Secondary Phase Separation in an Epoxy Resin Modified with Polyethersulfone
Authors: Tang Xiaolin , Zhang Linxia , Wang Tao , Yu Yingfeng , Gan Wenjun , Li Shanjun
Published: July 2004

Summary: The evolution of the morphologies in blends of epoxy/4,4′‐methylenebis(2,6‐dimethylaniline)/polyethersulfone was followed by time‐resolved light scattering, optical microscopy and scanning electron microscopy. The results suggest that, once the diffusion of epoxy molecules cannot follow the geometrical growth, a secondary phase separation occurs, even in the droplet morphology, in which the size of the epoxy‐rich domain grows as usual. The viscoelastic effect of polyethersulfone is also discussed.

Development of morphologies followed by OM: bicontinuous phase separation in the PES‐15.9 blend cured at 140 °C after 80 s.

magnified image

Development of morphologies followed by OM: bicontinuous phase separation in the PES‐15.9 blend cured at 140 °C after 80 s.
An integral equation method for a boundary value problem in superconductivity
Authors: Heese Harald
Published: July 2004

We present a mathematical model for transport current carrying superconductors in terms of a boundary value problem for the Laplace equation. A uniqueness and existence result is given via a boundary integral equation method in a Hölder space setting. It's numerical solution is described using a combined collocation method and quadrature rule approach including a convergence analysis and numerical examples. Copyright © 2004 John Wiley & Sons, Ltd.
Coupling of flow simulation and structural analysis for glass‐filled thermoplastics
Authors: Foss Peter H.
Published: July 2004

In the automotive industry, glass‐filled thermoplastics are used in air intake manifolds, radiator tanks, and many other parts. Plastic parts have many advantages over metal parts including mass, design flexibility and parts consolidation. However, widespread application of glass‐filled thermoplastic materials has been limited in many cases by the inability to accurately predict performance and durability. Fiber‐filled injection‐molded parts contain complex fiber orientation patterns. This fiber orientation state affects material properties including elastic modulus and strength and part properties including shrinkage and warpage. Tremendous amounts of time and money can be saved if one can predict the moldability and mechanical properties of a part at the design stage. In this work, we present a method where commercially available injection molding and structural analysis software may be coupled together with appropriate material property data to improve prediction of structural performance for parts molded from short glass fiber‐filled plastics. In addition, we compare the experimental and predicted performance based on simple equations and complex finite element calculations. Two major conclusions may be drawn from this work. In general, the assumption of geometric nonlinearity must be made. Also, an orthotropic material model is generally more robust and accurate than an isotropic analysis. Polym. Compos. 25:343–354, 2004. © 2004 Society of Plastics Engineers.
Rate‐dependent compressive behavior of unidirectional carbon fiber composites
Authors: Salvi Amit G. , Waas Anthony M. , Caliskan Ari
Published: July 2004

Unidirectional carbon fiber stitched composites were subjected to off‐axis compression under static and low‐velocity impact loading. Specimens were cut such that the fibers were at angles of 15°, 30°, 45° and 60° to the direction of loading. A modified compression fixture was used to carry out the tests. Static tests were carried out on a hydraulically activated MTS loading frame, where specimens were subjected to displacement controlled loading. Low‐velocity impact tests were conducted on a drop tower facility. A three‐strain‐gauge rosette was used to measure global strains. Load was measured using a load cell. Owing to the unique microstructure of the specimens, a modified three‐parameter characterization of the inelastic response was used, and the constants associated with this characterization were determined uniquely. Independently, Iosipescu shear tests were carried out to determine the shear response of the material under static and low‐velocity impact conditions. The shear response so determined was checked against the off‐axis test results. It is shown that rate‐dependent interfacial effects are predominant in these materials. Polym. Compos. 25:397–406, 2004. © 2004 Society of Plastics Engineers.
Fatigue crack initiation and propagation in polyamide‐6 and in polyamide‐6 nanocomposites
Authors: Bellemare Simon C. , Bureau Martin N. , Denault Johanne , Dickson J. Ivan
Published: July 2004

Recent developments in polymer nanocomposites have led to improvements in conventional short‐term, but the long‐term mechanical properties have received little attention. The objective of the present study was to characterize the effect of nanoparticles on the fatigue crack initiation and propagation mechanisms and on the fatigue properties of polyamide‐6 (PA6) nanocomposite (PA6NC) prepared byin situpolymerization with montmorillonite clay. Two approaches were employed: fatigue life measurements and crack growth monitoring. Compared with non‐filled PA6 at the same stress amplitude, the number of cycles to fracture was higher for the nanocomposite, which suggests an increase in the intrinsic resistance of the material to crack initiation. However, the crack growth rate results indicated that nanoparticles decreased the resistance to crack propagation. Post‐fatigue fractographic observations indicated a change in the fatigue crack propagation mechanism resulting from the addition of nanoparticles, primarily attributed to the increase in yield stress, which favors the development of a fibrillated deformation zone. The fibrillation process in the relatively high crack propagation rate regime appeared to be preceded by plastic deformation at approximately constant volume. Most of the effect of nanoparticles on the fatigue behavior and properties results probably from the mechanical reinforcement on the microstructure and its effect on the yield stress and Young's modulus rather than from the effect of the inorganic filler to act as a stress concentrator. Polym. Compos. 25:433–441, 2004. © 2004 Society of Plastics Engineers.
Fatigue testing of polymer membranes
Authors: Mackin Thomas J. , Vernon Paul J. , Begley Matthew R.
Published: July 2004

This paper presents a new impression method for fatigue testing polymer membranes that circumvents many of the problems associated with traditional uniaxial testing of thin, compliant films. The proposed test geometry subjects the polymer membrane to a biaxial stress state by displacing the center of a clamped circular specimen with a spherical indenter. The initiation of fatigue cracks in the membrane is monitored using optical and/or infrared sensing. Finite element and non‐linear membrane theory models, which take into account large‐displacement kinematics, non‐linear material behavior and friction between the indenter and membrane, are used to establish connections between the applied indenter displacement, or load, and the stress in the film. A key result is a closed‐form relationship between applied load and membrane stress, which can be used for a wide range of friction and material response. The broadly applicable approach is demonstrated using two types of laminated polymer membranes. Polym. Compos. 25:442–450, 2004. © 2004 Society of Plastics Engineers.
Solvation effects in the heterolyses of 3‐X‐3‐methylpentanes (X = Cl, Br, I)
Authors: Martins Filomena , Leitão Ruben Elvas , Moreira Luís
Published: July 2004

A comparative study of the heterolysis reactions of 3‐X‐3‐methylpentanes (X = Cl, Br, I) in a set of protic and aprotic solvents was performed at 25.00°C. Rate constant values were correlated with solvent descriptors using the TAKA multiparametric equation. Our results point towards a decrease in both hydrogen bond donor acidity (electrophilicity) and hydrogen bond acceptor basicity (nucleophilicity) contributions, and towards an increase in the dipolarity/polarizability term on going from the chloride substrate to iodide. These features suggest the formation of an increasingly early transition state, in contrast to the classical Hughes–Ingold rationale, but in agreement with the Hammond postulate. Furthermore, there seems to be no evidence for a shift in solvation from an electrophilic (or anionic) mode in the chloride substrate to a nucleophilic (or cationic) mode in the iodide, as claimed by some authors. Copyright © 2004 John Wiley & Sons, Ltd.
Chemistry of protonated species in gaseous environments
Authors: Chiavarino Barbara , Crestoni Maria E. , Fornarini Simonetta
Published: July 2004

An overview is presented of gas‐phase studies on the structure and reactivity of protonated species from the authors' research. Specific problems have been addressed operating in different gaseous environments, either in radiolytic systems at atmospheric pressure, enabling the NMR characterization of the neutral end products of gas phase ion–molecule reactions, or in low‐pressure FT‐ICR mass spectrometry, where ions can be trapped and characterized by their reactivity or spectroscopic features. Proton transfer reactions have revealed the role of competing acidic sites leading to biologically relevant C7H7O. radical species and of competing basic sites in substituted benzenes. Proton transfer reactions have also been used as a tool to form elusive cations, e.g. c‐C3H, modulating the reaction energetics, and to unveil the structure and occurrence of degenerate isomerization processes within the benzenium ion. Copyright © 2004 John Wiley & Sons, Ltd.
Substituent and solvent effects on the N‐2—N‐3 hindered rotation of cis‐1,3‐diphenyltriazenes
Authors: Barra Mónica , Srivastava Sonali , Brockman Eleanor
Published: July 2004

Laser‐flash photolysis techniques were applied to investigate the dependence of the rotational barrier about the N‐2—N‐3 bond of symmetrically 4,4′‐disubstituted cis‐1,3‐diphenyltriazenes on substituents and solvents. The increase in the rotational barrier with increasing ability of the 4‐substituent to withdraw electrons implies the intramolecular process to be more susceptible to the electronic character of the aryl group attached to N‐1 than of that bonded to N‐3. Furthermore, the increase in the rotational barrier with decreasing solvent polarity implies an increase in dipole moment on rotation from the ground state to the transition state. Copyright © 2004 John Wiley & Sons, Ltd.
Boron trifluoride activated enaminocarbonyl compounds: the influence of intermolecular interactions on theab initiodetermination of structures and vibrational spectra
Authors: Nikolai Joachim , Maas Gerhard , Taubmann Gerhard
Published: July 2004

The structures of the BF3–enaminoaldehyde adducts3a,bhave been determined by quantum‐chemical calculations employing Hartree‐Fock, Møller‐Plesset and density functional methods. The length of the coordinative BO bond ranges between 1.59 and 1.62 Å. The BSSE‐free energy of the BO bond ranges between −14.7 and −16.9 kcal/mol. Taking into account hydrogen bonds and dispersion forces between two molecules of3a,bin the dimeric structure4reduces the BO bond length significantly (BO: 1.52–1.57 Å) thereby reproducing the BO bond length found in the x‐ray structure of1(BO: 1.49 Å) with much better accuracy. Using the calculated IR and Raman spectra of the dimers4as reference, the BO band in the experimental spectra can be assigned. Our approach seems to be of value in discussions comparing structural features gained from gas phaseab initiocalculations and solid state x‐ray structures involving strong dipolar structures which allow for various intermolecular interactions. Copyright © 2004 John Wiley & Sons, Ltd.
From the conformation of a single molecule to physical networks in highly interacting polymers: A small‐angle neutron study
Authors: Perahia Dvora , Jiao Xuesong , Traiphol Rakchart
Published: July 2004

Small‐angle neutron scattering has been used to study the conformation and structure of highly interacting macromolecules in complex fluids. The evolution of the structure has been investigated from the conformation of a single molecule through an association process to the formation of physical networks. Two highly interacting polymers, an ionic polymer (consisting of a perfluorinated backbone and an ionizable hydrophilic side chain dissolved in water/alcohol mixtures) and rodlike, highly conjugated phenylene ethylene molecules (dissolved in toluene), have been studied. Highly interacting polymers often form relatively long lasting physical networks with increasing polymer concentration. The driving force, however, is system‐specific, and so are the micellar systems and physical networks formed. Although the two families of polymers under consideration are entirely different chemically, their strong interaction, either ionic or through π–π coupling, results in similarities in the complex fluids formed when they are dissolved in solutions. These include elongated configurations in dilute solutions, association into micelles, and eventually coalescence into physical networks. The ionic polymers form durable stable networks, whereas the rodlike polymers form a fragile, gel‐like phase. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3165–3178, 2004
Phase behavior of the polybutadiene–polystyrene diblock copolymer with the addition of the nonselective solvent dichlorobenzene in temperature and pressure fields
Authors: Abbas Basil , Schwahn Dietmar , Willner Lutz
Published: July 2004

Thermal composition fluctuations were measured in a polybutadiene–polystyrene diblock copolymer with small‐angle neutron scattering as a function of the temperature, pressure, and solvent content. The solvent was dichlorobenzene. In particular, we determined the phase diagram, the Flory–Huggins parameter, and the Ginzburg parameter. The two latter parameters were determined in terms of a theory by Fredrickson and Helfand from the susceptibility at an elevated temperature in the disordered regime. These parameters showed an overall linear decrease with pressure and a minimum at a 10% solvent content. The ordering temperature could be sufficiently well described by the theory of concentrated solutions. These results were consistent with corresponding experiments on a polybutadiene–polystyrene blend, for which the compensation of the free volume was observed by the solvent molecules. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3179–3190, 2004
Validation of a questionnaire for self‐assessment of sexual function and vaginal changes after gynaecological cancer
Authors: Jensen Pernille T. , Klee Marianne C. , Thranov Ingrid , Groenvold Mogens
Published: July 2004

The Sexual function‐Vaginal changes Questionnaire (SVQ), was developed to investigate sexual and vaginal problems in gynaecological cancer patients. The instrument consists of 20 core items, measuring sexual interest, lubrication, orgasm, dyspareunia, vaginal dimensions, intimacy, sexual problems of partner, sexual activity, sexual satisfaction, and body image. Seven additional items assessing current levels of sexual and vaginal problems compared to pre‐diagnosis are intended to be used only once in longitudinal studies. The SVQ was validated in two ways: first, the comprehensibility of each item was investigated through combined quantitative and qualitative assessment of patient‐observer agreement in 75 gynaecological cancer patients, second, multitrait analyses and principal component analyses were applied to responses from 257 patients with cervical cancer to investigate the scale properties. The level of agreement between the patients' and the observer's ratings was high (median overall agreement 0.84, range 0.46–1.00; median kappa: 0.80, range 0.52–1.00). From the 10 items applicable to all patients, three scales were hypothesized: intimacy, sexual interest and global sexual satisfaction. For sexually active respondents an additional two scales were hypothesized: vaginal changes and sexual functioning. The psychometric analyses confirmed these scales. The internal consistency of the scales ranged 0.76–0.83 (Cronbach's alpha). The study supports the validity and reliability of the SVQ. Copyright © 2003 John Wiley & Sons, Ltd.
Interest in services among prostate cancer patients receiving androgen deprivation therapy
Authors: Shapiro Pamela J. , Coyne James C. , Kruus Linda K. , Palmer Steven C. , Vaughn David J. , Malkowicz S. Bruce
Published: July 2004

Treatment side effects and decreased quality of life associated with androgen deprivation therapy (ADT) suggest the need for supportive services for prostate cancer (PC) patients receiving ADT. Nonetheless, uptake of services is low, suggesting that PC patients' preferences are not being addressed. We examined interest in supportive services and predictors of interest among 118 PC patients receiving ADT. Overall interest in services was associated with lower quality of life (p=0.01). The majority of participants expressed interest in informational services (70%), with a minority (22%) expressing interest in psychosocial services. Interest in psychosocial services was associated with younger age (p=0.02), and shorter duration of ADT (p<0.04), but was unrelated to psychological distress or social support. Although most men (68%) reported that they would prefer not to take medication for depression, 75% would do so if advised by their physician. Overall, results suggest that PC patients on ADT prefer individualized informational support. Substantial interest (61%) in Oncolink, an internet‐based informational resource, suggests the Internet may provide an acceptable mode of service delivery. Health care providers should consider integrating increased informational support into routine care and, more generally, consider patient preferences in prioritizing and designing support services. Copyright © 2003 John Wiley & Sons, Ltd.
Longitudinal course of depression, fatigue, and quality of life in patients with high risk melanoma receiving adjuvant interferon
Authors: Trask Peter C. , Paterson Amber G. , Esper Peg , Pau Jason , Redman Bruce
Published: July 2004

Purpose: Treatment of malignant melanoma with interferon‐α has been associated with a variety of side effects ranging from fatigue to depression, and a concomitant impact on quality of life (QOL), in a variety of case reports and cross‐sectional clinical trials. Few, if any, studies have been conducted with the express purpose of assessing the longitudinal course of depression, fatigue, and QOL before and during interferon therapy.

Description of study: The current study reports on 16 patients who were assessed at 6 points in time: baseline, post high dose, and 1, 2, 3, and 6 months post high dose treatment with interferon‐α with the Brief Symptom Inventory, Beck Depression Inventory, Revised Piper Fatigue Scale, and Functional Assessment of Cancer Therapy‐Biological Response Modifiers.

Results: Results revealed consistent changes from baseline through 6 month assessment. Specifically, increased somatic complaints, depression, and fatigue were observed on the BSI, BDI, and RPFS, respectively. Additional reductions in QOL on the FACT‐BRM were also identified.

Clinical implications: The findings suggest that IFN has a significant effect on QOL, but that it may be the somatic symptoms of fatigue that contribute to changes on measures of mood. Limiting the amount of fatigue and depression would appear to be significant if individuals are to successfully complete IFN therapy. Copyright © 2003 John Wiley & Sons, Ltd.
Repressive coping before and after diagnosis of breast cancer
Authors: Zachariae Robert , Jensen Anders Bonde , Pedersen Christina , Jørgensen Michael Martini , Christensen Søren , Lassesen Berit , Lehbrink Melsene
Published: July 2004

Objective: The aim was to investigate to which extent emotional repression is a premorbid coping tendency of cancer patients and/or a coping response to the threat posed by a cancer diagnosis. The results of one previous study of breast cancer patients suggest the latter possibility, and our aim was to replicate and extend these findings.

Methods: Of 646 women referred to mammographic examination for breast cancer, 71 women were diagnosed with primary breast cancer. Repressive coping, defined as having high scores on defensiveness (Marlowe–Crowne Social Desirability Scale) and low scores on anxiety (Taylor Manifest Anxiety Scale), was measured (1) before, (2) 4 weeks after, and (3) 12 weeks after diagnosis. The women were not aware of their disease status before the examination, and there were no significant differences between groups in their perceived risk of having breast cancer.

Results: Four weeks after diagnosis, increased repression (p<0.01) was found in the group of women diagnosed with breast cancer but not in women without cancer, with women with a breast cancer diagnosis being 1.5 times more likely to be repressive than women with cancer. There were no group differences in defensiveness, anxiety, or repression before diagnosis and 12 weeks after diagnosis. When controlling for repressive coping prior to diagnosis, age, and other demographic factors with a multiple, logistic regression, only cancer diagnosis (odds ratio: 2.39; p<0.05) and having biological children (odds ratio: 2.83; p< 0.02) emerged as significant predictors of repressive coping 4 weeks after diagnosis. Before diagnosis, only higher age predicted later diagnosis of breast cancer.

Conclusion: Previously found higher repression in cancer patients vs. controls could be a response to the threat associated with cancer diagnosis and may not necessarily reflect premorbid differences. Copyright © 2003 John Wiley & Sons, Ltd.
Electronic spectra of [(CH3)2NH2]5Cd2CuCl11 crystals
Authors: Kapustianik V. , Batiuk A. , Czapla Z. , Podsiadła D. , Czupiński O.
Published: July 2004

The temperature evolution of Cu2+ ion environment in the solid solutions of ((CH3)2NH2)5Cd2CuCl11 is studied on the basis of absorption spectroscopy data. For the detailed analysis of experimental data the special program package Crys Tool 1.0 based on quantum‐mechanical models, first of all on the model of normalized spherical harmonics (NSH), has been employed. It has been found that similarly to the crystal of ((CH3)2NH2)5Cd3Cl11 (DMACC) the investigated solid solution contains tetragonally distorted octahedral metal–halogen complexes of two types and the degree of their distortion is changed considerably at the temperatures of phase transitions (PTs). The parameters of crystal field, angular overlap model, as well as the copper–chlorine distances, show continuous changes at T1 = 176 K that should be related to the second‐order transition, whereas the jump‐like anomalies of the spectral parameters at T2 = 115 K (on cooling) are characteristic of the first‐order PTs. Introduction of the copper ions into the structure of the host DMACC crystal induces the shifts of these PTs toward low temperatures by 3.5 and 5 K, respectively. The observed structural changes around T0 = 313 K are connected with a complex co‐operative effect involving weakening of the hydrogen bonds and modification of the Jahn–Teller distortion with temperature. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
The in vitro antioxidant and antimicrobial activities of the essential oil and methanol extracts of Achillea biebersteini Afan. (Asteraceae)
Authors: Sökmen Atalay , Sökmen Münevver , Daferera Dimitra , Polissiou Moschos , Candan Ferda , Ünlü Mehmet , Akpulat H. Aşkın
Published: July 2004

The essential oil and methanol extracts from A. biebersteinii Afan. (Asteraceae) were evaluated for their antimicrobial and antioxidant activities in vitro. The oil showed stronger antimicrobial activity than the extracts. Their antioxidant features were also evaluated using diphenyl‐1‐picrylhydrazyl (DPPH), inhibition of superoxide and hydroxyl radicals and inhibition of the lipid peroxidation assays. Particularly, polar subfraction of the methanol extract showed antioxidant activity. The GC‐MS analysis of the oil has resulted in the identiﬁcation of 23 components; piperitone, eucalyptol, camphor, chrysanthenone and borneol were the main components. Antimicrobial activity tests carried out with the fractions of the oil showed that the activity was mainly observed in those containing eucalyptol and camphor, in particular, followed by borneol and piperitone. Copyright © 2004 John Wiley & Sons, Ltd.
Antifungal constituents of Clytostoma ramentaceum and Mansoa hirsuta
Authors: Rocha Alessandra Duarte , de Oliveira Alaíde Braga , de Souza Filho José Dias , Lombardi Júlio Antônio , Braga Fernão Castro
Published: July 2004

Ethanol extracts of Clytostoma ramentaceum Bur. & K. Schum and Mansoa hirsuta DC. (Bignoniaceae) inhibited the growth of standardized cultures of Aspergillus niger and Fusarium oxysporum, at concentrations of 400 µg and 500 µg, in bioautographic assays. The activity‐guided fractionation of C. ramentaceum extract afforded ursolic acid and 2‐(3′,4′‐dihydroxyphenyl) ethanol, both active against the test fungi (100 µg). These compounds are reported for the ﬁrst time in C. ramentaceum and were not detected in M. hirsuta extract, according to HPLC analysis. The bioguided study of M. hirsuta resulted in ﬁve active fractions (100 to 200 µg), whose GC‐MS analysis allowed us to identify 11 compounds, mostly alkanols and alkanodiols, that may be regarded as the antifungal constituents of M. hirsuta. Copyright © 2004 John Wiley & Sons, Ltd.
Biological screening of Nigella damascena for antimicrobial and molluscicidal activities
Authors: Fico G. , Panizzi L. , Flamini G. , Braca A. , Morelli I. , Tomè F. , Cioni P. L.
Published: July 2004

The essential oil, various extracts at different polarity, fractions, and pure compounds obtained from Nigella damascena plants and seeds were screened for biological activity. Antimicrobial tests showed the essential oil to be active only against Gram positive bacteria; among the extracts, the BuOH was active against Pseudomonas aeruginosa and Staphylococcus aureus. Molluscicidal activity was absent. Copyright © 2004 John Wiley & Sons, Ltd.
Lepidium peruvianum chacon restores homeostasis impaired by restraint stress
Authors: López‐Fando A. , Gómez‐Serranillos M. P. , Iglesias I. , Lock O. , Upamayta U. P. , Carretero M. E.
Published: July 2004

Lepidium peruvianum root has been traditionally utilized by native Peruvians, since before the time of the Incas, for both nutritional and putative medicinal purposes as an adaptogen and also to enhance fertility in humans and animals. The present research was conducted to evaluate the anti‐stress activity of the methanolic extract of Lepidium peruvianum. The drug is capable of attenuating or even eliminating variations in homeostasis produced by stress since it reduces or abolishes stress‐induced ulcers, elevated corticosterone levels, the reduction of glucose and the increase in the weight of adrenal glands produced by stress. It also eliminates the decrease in free fatty‐acids (FFA) in plasma produced by stress and we obtain a positive result in the forced‐swimming test. Thus, it did not appear to affect restraint stress‐induced immunosuppression. Copyright © 2004 John Wiley & Sons, Ltd.
Antiviral activity of the red marine alga Ceramium rubrum
Authors: Serkedjieva Julia
Published: July 2004

An extract from the red marine alga Ceramium rubrum (Huds.) Ag. from the Bulgarian Black Sea seacoast considerably inhibited the reproduction of inﬂuenza viruses type A and B in vitro and in ovo. The virus‐induced cytopathogenic effect (CPE), infectious virus yields and the production of hemagglutinin were all reduced at non‐toxic concentrations of the extract. The virus‐inhibitory effect was selective, dose‐related and strain‐speciﬁc; selectivity indices ranged 9.5–68.3. The inhibition affected adsorption as well as the intracellular stages of viral replication. The extract inhibited also the reproduction of herpes simplex virus (HSV) type 1 and type 2 in cell cultures. The preparation exhibited a strong HSV‐inactivating activity. Copyright © 2004 John Wiley & Sons, Ltd.
Evaluation of the gastric antiulcerogenic effects of Portulaca oleracea L. extracts in mice
Authors: Karimi Gholamreza , Hosseinzadeh Hossein , Ettehad Negin
Published: July 2004

Portulaca oleracea is commonly used in Iranian folk medicine. The aqueous and ethanolic extracts were studied in mice for their ability to inhibit gastric lesions induced by HCl or absolute ethanol. In addition, their effects on gastric acid secretion were measured. Both extracts showed a dose‐dependent reduction in severity of ulcers. The highest dose of extracts exerted similar activity to sucralfate. The oral and intraperitoneal administration of extracts reduced the gastric acidity in pylorus‐ligated mice. These results suggest that Portulaca oleracea has gastroprotective action and validates its use in folk medicine for gastrointestinal diseases. Copyright © 2004 John Wiley & Sons, Ltd.
SPC with Applications to Churn Management
Authors: Pettersson Magnus
Published: July 2004

The process of a customer replacing one provider of a service or merchandise for another is called a churn. In competitive business environments, such as telecommunications, insurance, banking, hotels and mail order, customers can easily leave one company—and they really do. Since the cost of recruiting new customers is higher than the cost of retaining them, it is crucial for companies in these trades to monitor their customer population in order to keep churn rates low. Statistical process control (SPC) methods are developed to cover the needs of monitoring industrial processes and intensive care patients. They are based on procedures where data are analysed automatically and on‐line. When results indicate that the process is out of control, an alarm alerts an engineer or physician, who can take corrective action in order to get the process back under control. This paper discusses the use of SPC methods as a means to enhance precision in detecting increasing churn rates. We show that SPC methods can give market analysts a powerful tool for tracking customer movements and churn. An early warning system (EWS), based on the same ideas as used in process industries, will give foresight and a longer time to react against churn, hence providing an advantage over competitors. In the examples discussed in this paper we monitor usage in order to detect decreasing volumes that indicate churn. Data were extracted from internal databases, and analysed and reported on‐line. We conclude that the potential improvement by using SPC methods in churn management is high. Copyright © 2004 John Wiley & Sons, Ltd.
Modelling Operational Losses: A Bayesian Approach
Authors: Giudici Paolo , Bilotta Annalisa
Published: July 2004

The exposure of banks to operational risk has increased in recent years. The Basel Committee on Banking Supervision (known as Basel II) has established a capital charge to cover operational risks other than credit and market risk. According to the advanced methods defined in ‘The New Basel Capital Accord’ to quantify the capital charge, in this paper we present an advanced measurement approach based on a Bayesian network model that estimates an internal measure of risk of the bank. One of the main problems faced when measuring the operational risk is the scarcity of loss data. The methodology proposed solves this critical point because it allows a coherent integration, via Bayes' theorem, of different sources of information, such as internal and external data, and the opinions of ‘experts’ (process owners) about the frequency and the severity of each loss event. Furthermore, the model corrects the losses distribution by considering the eventual relations between different nodes of the network that represent the losses of each combination of business line/event type/bank/process and the effectiveness of the corresponding internal and external controls. The operational risk capital charge is quantified by multiplying the value at risk (VaR) per event, a percentile of the losses distribution determined, by an estimate of the number of losses that may occur in a given period. Furthermore, it becomes possible to monitor the effectiveness of the internal and external system controls in place at the bank. The methodology we present has been experimented as a pilot project in one of the most important Italian banking groups, Monte dei Paschi di Siena. Copyright © 2004 John Wiley & Sons, Ltd.