bluuebunny/crossref_metadata_2025 huggingface dataset:
Stakeholder partnerships as collaborative policymaking: Evaluation criteria applied to watershed management in California and Washington
Authors: Leach William D. , Pelkey Neil W. , Sabatier Paul A.
Published: October 2002

Public policymaking and implementation in the United States are increasingly handled through local,
consensus‐seeking partnerships involving most affected stakeholders. This paper formalizes the concept
of a stakeholder partnership, and proposes techniques for using interviews, surveys, and documents to measure
each of six evaluation criteria. Then the criteria are applied to 44 watershed partnerships in California and
Washington. The data suggest that each criterion makes a unique contribution to the overall evaluation, and
together the criteria reflect a range of partnership goals—both short‐term and long‐term,
substantive and instrumental. Success takes time—frequently about 48 months to achieve major milestones,
such as formal agreements and implementation of restoration, education, or monitoring projects. Stakeholders
perceive that their partnerships have been most effective at addressing local problems and at addressing
serious problems—not just uncontroversial issues, as previously hypothesized. On the other hand, they
perceive that partnerships have occasionally aggravated problems involving the economy, regulation, and threats
to property rights. © 2002 by the Association for Public Policy Analysis and Management.
Postmarketing drug dosage changes of 499 FDA‐approved new molecular entities, 1980–1999
Authors: Cross James , Lee Howard , Westelinck Agnes , Nelson Julie , Grudzinskas Charles , Peck Carl
Published: October 2002

Purpose

Risks and benefits of marketed drugs can be improved by changing their labels to optimize dosage regimens for indicated populations. Such postmarketing label changes may reflect the quality of pre‐marketing development, regulatory review, and postmarketing surveillance. We documented dosage changes of FDA‐approved new molecular entities (NMEs), and investigated trends over time and across therapeutic groups, on the premise that improved drug development methods have yielded fewer postmarketing label changes over time.

Methods

We compiled a list of NMEs approved by FDA from 1 January 1980 to 31 December 1999 using FDA's website, Freedom of Information Act request, and PhRMA (Pharmaceutical Research and Manufacturers of America) database. Original labeled dosages and indicated patient populations were tracked in labels in thePhysician's Desk Reference®. Time and covariate‐adjusted risks for dosage changes by 5‐year epoch and therapeutic groups were estimated by survival analysis.

Results

Of 499 NMEs, 354 (71%) were evaluable. Dosage changes in indicated populations occurred in 73 NMEs (21%). A total of 58 (79%) were safety‐motivated, net dosage decreases. Percentage of NMEs with changes by therapeutic group ranged from 27.3% for neuropharmacologic drugs to 13.6% for miscellaneous drugs. Median time to change following approval fell from 6.5 years (1980–1984) to 2.0 years (1995–1999). Contrary to our premise, 1995–1999 NMEs were 3.15 times more likely to change in comparison to 1980–1984 NMEs (p = 0.008, Cox analysis).

Conclusions

Dosages of one in five NMEs changed, four in five changes were safety reductions. Increasing frequency of changes, independent of therapeutic group, may reflect intensified postmarketing surveillance and underscores the need to improve pre‐marketing optimization of dosage and indicated population. Copyright © 2002 John Wiley & Sons, Ltd.
Self‐esteem: a behavioural genetic perspective
Authors: Neiss Michelle B. , Sedikides Constantine , Stevenson Jim
Published: October 2002

Self‐esteem, the affective or evaluative appraisal of one's self, is linked with adaptive personality functioning: high self‐esteem is associated with psychological health benefits (e.g. subjective well‐being, absence of depression and anxiety), effective coping with illness, and satisfactory social relationships. Although several pathways have been hypothesized to effect within‐family transmission of self‐esteem (e.g. parenting style, family relationship patterns), we focus in this article on genetic influences. Genetic studies on both global and domain‐specific self‐esteem and on both level and stability of self‐esteem converge in showing that (i) genetic influences on self‐esteem are substantial, (ii) shared environmental influences are minimal, and (iii) non‐shared environmental influences explain the largest amount of variance in self‐esteem. We advocate that understanding of current issues in self‐esteem research will be enriched by including behavioural genetic approaches. Copyright © 2002 John Wiley & Sons, Ltd.
Solvent effects in the Grignard reaction with alkynes
Authors: Tuulmets A. , Pällin V. , Tammiku‐Taul J. , Burk P. , Raie K.
Published: October 2002

Kinetic studies were carried out on the reaction of phenylmagnesium bromide with hex‐1‐yne in diethyl ether, and in binary mixtures of diethyl ether with toluene, chlorobenzene and dichloromethane. The reaction was accelerated by addition of non‐donating solvents. The replacement of a coordinated solvent molecule by the alkyne is necessary for the reaction to proceed, according to density functional theory (DFT) calculations with B3LYP/6–31 + G* method. The non‐donating solvents accelerate the reaction by shifting the replacement equilibrium in favour of the complex formation. An analysis in terms of the Koppel–Palm equation revealed a rate decrease with increase in solvent polarity and polarizability. Copyright © 2002 John Wiley & Sons, Ltd.
Correlation analysis of reactivity in oxidation of substituted benzyl alcohols by tetrabutylammonium tribromide
Authors: Kumar Ashok , Sharma Pradeep K. , Banerji Kalyan K.
Published: October 2002

Oxidation of benzyl alcohol and some ortho‐, meta‐ and para‐monosubstituted benzyl alcohols by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid leads to the formation of corresponding benzaldehydes. The reaction is first order each in TBATB and the alcohol. The oxidation of [1,1‐2H2]benzyl alcohol (PhCD2OH) exhibited a substantial kinetic isotope effect. Addition of tetrabutylammonium chloride or potassium bromide did not affect the rate. Tribromide ion has been postulated as the reactive oxidizing species. The reaction rate increases with increase in the polarity of the solvent. The rates of oxidation of meta‐ and para‐substituted benzyl alcohols showed excellent correlation in terms of Charton's triparametric LDR, equation whereas the oxidation of ortho‐substituted benzyl alcohols correlated best with the LDRS equation. The oxidation of para‐substituted benzyl alcohols is more susceptible to the delocalization effect than is the oxidation of ortho‐ and meta‐substituted compounds, which display a greater dependence on the field effect. The positive value of η suggests the presence of an electron‐deficient reaction centre in the rate‐determining step. The reaction is subject to steric acceleration by the ortho‐substituents. A suitable mechanism is proposed. Copyright © 2002 John Wiley & Sons, Ltd.
Reversible addition–fragmentation chain‐transfer polymerization: Unambiguous end‐group assignment via electrospray ionization mass spectrometry
Authors: Vana Philipp , Albertin Luca , Barner Leonie , Davis Thomas P. , Barner‐Kowollik Christopher
Published: October 2002

Electrospray ionization mass spectrometry was performed to identify the structure of polymeric methyl acrylates generated via the cumyl dithiobenzoate (CDB), cumyl p‐fluorodithiobenzoate (CPFDB), and 1‐phenylethyl dithiobenzoate (PEDB) mediated reversible addition–fragmentation chain‐transfer (RAFT) polymerizations. The relatively simple spectra clearly demonstrate the end groups of this living free‐radical polymerization technique. Only polymeric chains carrying one leaving group of the RAFT agent and the dithiobenzoate end group as the active RAFT center were discovered. Multiple‐stage mass spectrometric experiments and oxidation of the dithioester end group confirmed the structure of the generated polymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4032–4037, 2002
Long‐term rates of mass wasting in Mesters Vig, northeast Greenland: notes on a re‐survey
Authors: Carver Steve , Mikkelsen Naja , Woodward John
Published: October 2002

Re‐surveys of surviving mass‐wasting target lines established by A.L. Washburn in the late 1950s in the Mesters Vig area, northeast Greenland, are used to derive estimates of long‐term mass wasting in the area. Rates of 2.9–8.1 cm.yr−1 are calculated for a 2.5–3° slope and 1.5–30.4 cm.yr−1 for a gelifluction lobe on a 15–23° slope. Compared to Washburn's short‐term measurements for the same sites these long‐term rates suggest a general increase in the rate of mass wasting in the Mesters Vig area over the last 40 years. This increase may be related to a general pattern of climatic amelioration for the east coast of Greenland. Copyright © 2002 John Wiley & Sons, Ltd.
Active‐layer mapping at regional scales: a 13‐year spatial time series for the Kuparuk region, north‐central Alaska
Authors: Shiklomanov N. I. , Nelson F. E.
Published: October 2002

Results from extensive, spatially‐oriented field investigations conducted in the Kuparuk River region of north‐central Alaska were used in conjunction with a simple analytical procedure to provide a comprehensive analysis of active‐layer variability under contemporary climate. This approach, based on Stefan's solution to the heat‐conduction problem with phase change, uses air temperature as the forcing function. An edaphic parameter represents the landcover‐specific response of the ground thermal regime to such local factors as lateral variations in soil, vegetation and moisture conditions. Regional estimates of climatic conditions were used within the framework of the spatial active‐layer model to map active‐layer thickness over the Kuparuk region on an annual basis, yielding a 13‐year spatial time series of regional thaw‐depth estimates. Results indicate that high‐resolution active‐layer mapping at regional scales is feasible given moderate amounts of climatic and edaphic information, obtained through extensive active‐layer sampling at locations representative of a number of environmental conditions. The analysis of annual thaw‐depth fields indicates that interannual climatic variability causes significant changes in active‐layer thickness. Copyright © 2002 John Wiley & Sons, Ltd.
Pulmonary epithelial liquid absorption, expressed in relation to alveolar surface area, is reduced in fetal lambs following in utero tracheal occlusion
Authors: Davey M.G. , Hedrick H.L. , Mendoza J.M. , Kanai M. , Adzick N.S. , Flake A.W.
Published: October 2002

We examined the effect of accelerated lung growth, induced by in utero tracheal occlusion (TO), on lung liquid uptake in near‐term fetal sheep. In utero TO was performed in five fetal sheep at 110 days of gestation (term, ∼145 days); six SHAM operated fetuses served as controls. The rate of liquid movement across the pulmonary epithelium was measured, using a previously established technique, in anesthetized fetal sheep between 133–137 days of gestation during a 2‐hr adrenaline infusion (0.50 μg/min/kg, I.V.) and while lung luminal pressure was maintained at 5 mmHg.

The rate of fetal lung liquid uptake was linear in all fetuses (mean r2 < 0.97, n = 11). Mean values of lung liquid uptake expressed in relation to dry lung weight and luminal surface area of the right lung were significantly lower in TO fetuses (1.8 ± 0.3 mL/hr/g and 1.0 ± 0.2 mL/hr/m2) than in SHAM fetuses (2.6 ± 0.2 mL/hr/g and 1.8 ± 0.1 mL/hr/m2); surface area of the right lung was 140% greater in TO fetuses than in SHAM fetuses. There was a linear relationship between lung liquid uptake and pulmonary epithelial surface area in SHAM animals, but not in TO fetuses.

We hypothesize that loss of alveolar epithelial type‐II cells induced by increased levels of fetal lung expansion may impair alveolar liquid clearance in the perinatal period. Pediatr Pulmonol. 2002; 34:278–286. © 2002 Wiley‐Liss, Inc.
Clinical, physiologic, and roentgenographic changes after pneumonectomy in a boy with Macleod/Swyer‐James syndrome and bronchiectasis
Authors: Fregonese Laura , Girosi Donata , Battistini Elena , Fregonese Bruno , Risso Francesco M. , Bava Giovanni L. , Rossi Giovanni A.
Published: October 2002

Macleod/Swyer‐James syndrome is an uncommon and complex disease characterized by roentgenographic hyperlucency of one lung or lobe due to loss of the pulmonary vascular structure and to alveolar overdistension. This syndrome seems to be an acquired disease that follows viral bronchiolitis and pneumonitis in childhood. It must be differentiated from many other causes of unilateral lung “transradiancy” on the chest roentgenogram, such as those related to congenital bronchial and/or vascular abnormalities. We here describe an 11‐year‐old patient with Macleod/Swyer‐James syndrome and bronchiectasis resulting in severe recurrent bronchopulmonary infections. Despite the severe impairment of pulmonary function, the patient underwent resection of the right lung with progressive improvement of clinical and physiologic parameters. Pediatr Pulmonol. 2002; 34:412–416. © 2002 Wiley‐Liss, Inc.
Overlapping binding sites for trypsin and papain on a Kunitz‐type proteinase inhibitor from Prosopis juliflora
Authors: Franco Octávio L. , Grossi de Sá Maria F. , Sales Maurício P. , Mello Luciane V. , Oliveira Adeliana S. , Rigden Daniel J.
Published: October 2002

Proteinase inhibitors are among the most promising candidates for expression by transgenic plants and consequent protection against insect predation. However, some insects can respond to the threat of the proteinase inhibitor by the production of enzymes insensitive to inhibition. Inhibitors combining more than one favorable activity are therefore strongly favored. Recently, a known small Kunitz trypsin inhibitor from Prosopis juliflora (PTPKI) has been shown to possess unexpected potent cysteine proteinase inhibitory activity. Here we show, by enzyme assay and gel filtration, that, unlike other Kunitz inhibitors with dual activities, this inhibitor is incapable of simultaneous inhibition of trypsin and papain. These data are most readily interpreted by proposing overlapping binding sites for the two enzymes. Molecular modeling and docking experiments favor an interaction mode in which the same inhibitor loop that interacts in a canonical fashion with trypsin can also bind into the papain catalytic site cleft. Unusual residue substitutions at the proposed interface can explain the relative rarity of twin trypsin/papain inhibition. Other changes seem responsible for the relative low affinity of PTPKI for trypsin. The predicted coincidence of trypsin and papain binding sites, once confirmed, would facilitate the search, by phage display for example, for mutants highly active against both proteinases. Proteins 2002;49:335–341. © 2002 Wiley‐Liss, Inc.
Arbutus unedo induces endothelium‐dependent relaxation of the isolated rat aorta
Authors: Ziyyat Abderrahim , Mekhfi Hassane , Bnouham Mohamed , Tahri Abdelhafid , Legssyer Abdelkhaleq , Hoerter Jacqueline , Fischmeister Rodolphe
Published: October 2002

Arbutus unedo L. (Ericaceae) is used in oriental Morocco to treat arterial hypertension. We studied its vasodilator effect and mechanisms of action in vitro. The root aqueous extract of Arbutus (0.25 mg/mL) produced a relaxation of noradrenaline‐precontracted ring preparations of rat aorta with intact endothelium. Relaxation by Arbutus did not occur in specimens without endothelium and was inhibited by pretreatment with 100 μM NG‐methyl‐L‐arginine (L‐NMA), 10 μM methylene blue or 50 μM 1H‐[1,2,4] oxadiazolo [4,3‐a] quinoxaline‐1‐one (ODQ) but not by 10 μM atropine. These results suggest that Arbutus produces an endothelium‐dependent relaxation of the isolated rat aorta which may be mediated mainly by a stimulation of the endothelial nitric oxide synthase by mechanisms other than activation of muscarinic receptors. Copyright © 2002 John Wiley & Sons, Ltd.
Protection of DNA and microsomal membranes in vitro by Glycyrrhiza glabra L. against gamma irradiation
Authors: Shetty T. K. , Satav J. G. , Nair C. K. K.
Published: October 2002

The radioprotective effect of the root extract of Glycyrrhiza glabra L on lipid peroxidation in rat liver microsomes and plasmid pBR322 DNA was investigated. The extract was found to protect microsomal membranes, as evident from reduction in lipid peroxidation, and could also protect plasmid DNA from radiation‐induced strand breaks. Copyright © 2002 John Wiley & Sons, Ltd.
Resistance‐distance matrix: A computational algorithm and its application
Authors: Babić D. , Klein D. J. , Lukovits I. , Nikolić S. , Trinajstić N.
Published: October 2002

The distance matrix D, the resistance‐distance matrix Ω, the related quotient matrices D/Ω and Ω/D and the corresponding distance‐related and resistance‐distance‐related descriptors: the Wiener index W, the Balaban indices J and JΩ, the Kirchhoff index Kf, the Wiener‐sum index WS, and Kirchhoff‐sum index KfS are presented. A simple algorithm for computing the resistance‐distance matrix is outlined. The distance‐related and the resistance‐distance‐related indices are used to study cyclicity in four classes of polycyclic graphs: five‐vertex graphs containing a five‐cycle and Schlegel graphs representing platonic solids, buckminsterfullerene isomers and C70 isomers. Among the considered indices only the Kirchhoff index correctly ranks according to their cyclicity, the Schlegel graphs for platonic solids, C60 isomers, and C70 isomers. The Kirchhoff index further produces the reverse order of five‐vertex graphs containing a five‐cycle (which could be simply altered to the correct order by adding a minus sign to the Kirchhoff indices for these graphs). © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001
cis‐Diamminedichloropalladium and its interaction with guanine and guanine–cytosine base pair
Authors: Hill Glake A. , Forde Gareth , Gorb Leonid , Leszczynski Jerzy
Published: October 2002

Comprehensive ab initio calculations are performed on cis‐diamminedichloropalladium (cispd) at the HF, DFT, MP2, and CISD levels of theory. The results are compared to those obtained for cisplatin. The characteristics of the interactions of cispd with guanine and the guanine–cytosine (GC) base pair are also evaluated and compared to the interactions of cisplatin. Cispd causes similar geometric changes of the base as cis‐platinum when complexed to guanine. The palladium and platinum complexes also show similar characteristics when complexed to the GC base pair. However, this study revealed lower dissociation energy of the chlorine ligands and lower interaction energy of the cispd with guanine, which indicates areas of differences between the title Pd and Pt complexes. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002
Density functional embedded cluster calculations on Lewis acid centers of the α‐Al2O3(0001) surface: Adsorption of a CO probe
Authors: Nasluzov Vladimir A. , Rivanenkov Vladimir V. , Shor Alexey M. , Neyman Konstantin M. , Birkenheuer Uwe , Rösch Notker
Published: October 2002

We have investigated the adsorption of CO on the cation‐terminated (0001) surface of α‐Al2O3 with a generalized‐gradient density functional approach. We used cluster models that are consistently embedded in an elastic polarizable environment (EPE), employing a (classical) shell model scheme and bare pseudopotentials (Alpp*) for cations at the cluster boundary. The newly implemented EPE method was found to perform well for describing structure and adsorption properties of Lewis acidic centers of the polar (0001) surface known for its strong relaxation with respect to the bulk terminated geometry. The calculated data are stable with respect to the size of the cluster models. For the embedded stoichiometric clusters [Al4O6]/Al\documentclass{article}\pagestyle{empty}\begin{document}$_{6}^{\mathrm{pp}\ast}$\end{document} and [Al10O15]/Al\documentclass{article}\pagestyle{empty}\begin{document}$_{13}^{\mathrm{pp}\ast}$\end{document} of different structure, the adsorption induced shift Δν of the CO stretching vibration and the binding energy (BE) are 30–42 cm−1 and 0.38–0.47 eV, respectively. The results for the frequency shifts are in good agreement with the value of 39 cm−1 measured for CO/α‐Al2O3(0001) at low coverages. Judged by the frequency shift and the adsorption energy, the interaction of CO molecules with three‐coordinated Al3+ cations at the regular surface is very similar to that with Mg2+ corner sites of MgO polycrystallites, Δν=39 cm−1, BE=0.38 eV. © 2002 John Wiley & Sons, Inc. Int J Quantum Chem, 2002
Study of the electrospray ionization tandem mass spectrometry of sildenafil derivatives
Authors: Zhong Dafang , Xing Jie , Zhang Shuqiu , Sun Lu
Published: October 2002

A detailed analysis of the product ion spectrum generated from the protonated molecule of sildenafil (Viagra®) under multiple tandem mass spectrometry (ESI‐MSn) conditions using an ion‐trap mass spectrometer is reported. Molecular composition data of the fragment ions were obtained with the aid of comparisons of the multiple tandem mass spectra of eight sildenafil derivatives in two series, the structures of which are identical except for some substituted alkyl groups. Attempts have been made to provide rational pathways for the formation of the fragment ions from these protonated sildenafil derivatives. The structure‐fragmentation relationships will facilitate the characterization of the structures of other sildenafil analogs. Copyright © 2002 John Wiley & Sons, Ltd.
A multiagent reinforcement learning method based on the model inference of the other agents
Authors: Matsuno Yoichiro , Yamazaki Tatsuya , Matsuda Jun , Ishii Shin
Published: October 2002

This paper proposes a reinforcement learning method based on an actor‐critic architecture, which can be applied to multiagent competitive games. As an example, we deal with the card game “Hearts.” We introduce a method combining an actor‐critic learning and model inference of the other agents. A single Hearts game is divided into three stages, and three actors are prepared so that one of them determines actions separately in each stage. In the middle stage, in particular, actions are determined based on expected temporal‐difference error. Computer simulation results suggest the importance of the model inference of the other agents. © 2002 Wiley Periodicals, Inc. Syst Comp Jpn, 33(12): 67–76, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/scj.10110
Space‐time invariants and recognition of motions from arbitrary viewpoints
Authors: Sato Jun
Published: October 2002

The recognition of motions is very important for understanding dynamic actions and extracting events from video sequences. In this paper, we propose invariants on object motions, which can be extracted from image sequences, and are invariant even if the motions are viewed from arbitrary viewpoints. We call them space‐time invariants since they are defined under space‐time projections. We show that these invariants are very useful for extracting specific motions from video sequences. The proposed space‐time invariants are implemented and tested on real image sequences. © 2002 Wiley Periodicals, Inc. Syst Comp Jpn, 33(12): 38–46, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/scj.10147
A coterie‐based mutual exclusion algorithm for distributed systems allowing multiple process failures at arbitrary time
Authors: Takekawa Shigeki , Wakabayashi Shin'ichi , Koide Tetsushi
Published: October 2002

In this article, we propose a coterie‐based mutual exclusion algorithm for distributed systems allowing process failures at arbitrary time. The proposed algorithm is an extension of Maekawa's algorithm, which is a representative conventional method for distributed mutual exclusion based on coterie. The proposed algorithm realizes mutual exclusion by detecting process failures using timers, updating the coterie dynamically, and introducing the system to a state without failure. It has the following advantages. First, it inherits all advantages of Maekawa's algorithm, because it behaves in the same way as Maekawa's algorithm when there is no process failure. Also, it allowsk(<N;Nis the number of processes) process failures at arbitrary time, so the assumption on failure is close to real systems. Furthermore, it is assured that the updated coterie is an ND (nondominated) coterie if the initial coterie is an ND coterie. We also describe an extension of this algorithm to the case where failed processes are allowed to return to normal states. © 2002 Wiley Periodicals, Inc. Syst Comp Jpn, 33(12): 87–96, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/scj.1169
DNA sequencing with ToF‐SIMS
Authors: Arlinghaus H. F. , Ostrop M. , Friedrichs O. , Feldner J. , Gunst U. , Lipinsky D.
Published: October 2002

Nucleic acid chips are based on the method of sequencing by hybridization, where unknown DNA fragments are hybridized to complementary nucleic acid sequences that are immobilized on a solid surface in an array format. One novel approach is to use peptide nucleic acid (PNA) biosensor chips. These DNA analogue possess the ability to hybridize with complementary DNA sequences. Because the backbone of DNA contains phosphates as opposed to PNA that does not, a technique that identifies the presence of these phosphates in a molecular surface layer would allow unlabelled DNA fragments hybridized to complementary PNAs to be detected. We have successfully shown that time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) is a very useful tool for identifying hybridized DNA on PNA biosensor chips by detecting the phosphorus present in the DNA. ToF‐SIMS is also a very effective technique for studying the complexity of the immobilization and hybridization process. Copyright © 2002 John Wiley & Sons, Ltd.
Synthesis and characterization of nanophasic LaCoO3 powders
Authors: Armelao L. , Bandoli G. , Barreca D. , Bettinelli M. , Bottaro G. , Caneschi A.
Published: October 2002

Nanophasic LaCoO3 powders were synthesized from inorganic compounds both in molten chloride fluxes and by using a solution combustion synthesis procedure. The samples were prepared in air and underwent subsequent heat treatments in order to yield the perovskite crystalline phase. The composition and microstructure of the samples were investigated by XPS, x‐ray‐induced AES, x‐ray diffraction and electron paramagnetic resonance. Further information was gained by magnetic measurements. Nanophasic LaCoO3 powders with an average crystallite size of 35 nm were obtained. Copyright © 2002 John Wiley & Sons, Ltd.
Influence of the nature of the noble metal (Rh,Pt) on the low‐temperature reducibility of a Ce/Tb mixed oxide with application as TWC component
Authors: Blanco G. , Pintado J.M. , Bernal S. , Cauqui M.A. , Corchado M.P. , Galtayries A. , Ghijsen J. , Sporken R. , Eickhoff T. , Drube W.
Published: October 2002

Ceria‐based mixed oxides have proved to be good alternatives to pure ceria as redox materials for advanced three‐way catalysts. In this work, the behaviour of a Ce0.8Tb0.2O2−xmixed‐oxide sample and the corresponding oxide‐supported Rh and Pt samples has been investigated. Special attention has been paid to the low‐temperature redox response. Temperature‐programmed desorption (TPD), temperature‐programmed reduction and oxygen buffering capacity were used as experimental techniques. The evolution of reducibility was also followed by tunable high‐energy x‐ray photoemission spectroscopy, focussing on the surface information provided by Tb 3d and Ce 3d core levels. The oxidation state of both Ce and Tb was followed during ultrahigh vacuum annealing of the three samples up to 750 K. Comparison of the XPS spectra for the different samples before and after annealing showed that the Ce4+reduction was negligible but Tb4+was gradually reduced to Tb3+. Furthermore, the TPD and XPS experiments are in good agreement, with the highest reduction rate corresponding to the Rh/CeTbOxsample. Copyright © 2002 John Wiley & Sons, Ltd.
Surface analysis of PECVD organosilicon films for corrosion protection of steel substrates
Authors: Angelini E. , d'Agostino R. , Fracassi F. , Grassini S. , Rosalbino F.
Published: October 2002

This study deals with the surface and electrochemical characterization of mild steel surfaces after plasma‐enhanced chemical vapour deposition of organosilicon films, performed in order to increase corrosion resistance. Coating deposition was performed in a home‐made reactor with hexamethyldisiloxane–oxygen–argon mixtures of different compositions and at different input power values on as‐received specimens and after a pretreatment step in oxygen‐containing plasma. Surface and morphological characterization of coatings was performed by x‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy. To evaluate the protective effectiveness, electrochemical characterization of the coatings was carried out in sulphate‐containing solutions by electrochemical impedance spectroscopy.

Notwithstanding their low thickness of ∼1000 nm, the organosilicon films show protective effectiveness properties against corrosion. An increase of the impedance values, related to an increase in the protective effectiveness, has been observed on films obtained at increasing input power and after O2 plasma pretreatment of the substrate. As shown by FTIR data, the positive effect of increasing input power may be related to the progressive increase of the inorganic nature of the deposited coatings, i.e. increase in SiOx groups and decrease of sylanol groups. Furthermore, as shown by XPS analysis, the good corrosion behaviour of mild steels coated after O2 plasma pretreatment may be attributed to removal of the surface contamination, which improves adhesion of the SiOx film, and to enhancement of the surface oxidation degree. Copyright © 2002 John Wiley & Sons, Ltd.
Determination of surface nanostructure from analysis of electron plasmon losses in XPS
Authors: Yubero F. , Holgado J. P. , Barranco A. , González‐Elipe A. R.
Published: October 2002

We have explored the possibility of obtaining information about the surface nanostructure (i.e., how a given phase of material is distributed near to the surface region) from the analysis of loss plasmons that appear in the lower kinetic energy side of photoelectron and Auger peaks. First, we show an example where information is mainly obtained from the position of the plasmon peak. In practice, two‐dimensional growth of an Al2O3 deposit on SiO2 is deduced by identification of surface plasmon excitation due to electron transport of the corresponding Al KLL signal. Furthermore, a new method based on a quantitative (plasmon peak intensity) description of the single plasmon excitation that appears behind a photoelectron peak is proposed. This method has been applied to describe the growth mechanism of MgO deposited by evaporation on TiO2. Thus, it is shown that MgO grows with strong island formation according to the analysis. The consistency of the proposed method is supported by factor analysis of the loss structure behind the Mg 1s peak. Moreover, the validity of the proposed method has been checked using Tougaard background analysis for the same system. From these results, an alternative method, based on analysis of the plasmon structure observed behind x‐ray photoelectron peaks, is proposed for characterization of the nanostructure in this type of system. Copyright © 2002 John Wiley & Sons, Ltd.
Alteration of Ti 2p XPS spectrum for titanium oxide by low‐energy Ar ion bombardment
Authors: Hashimoto Satoshi , Tanaka Akihiro
Published: October 2002

Alteration of Ti 2p XPS spectra for TiO2 single crystal was measured during Ar ion sputtering. The acceleration voltage of Ar ion bombardment ranged from 10 V to 2 kV.

Components of Ti2+ and Ti3+ as reduced states have appeared, in addition to the Ti4+ state, after ion bombardment at 2 kV. However, although a small amount of Ti3+ has been observed in the case of 10 V bombardment, the Ti2+ component has not appeared. The intensities of the reduced states (Ti2+ and/or Ti3+) that have appeared at each acceleration voltage reach constant values after a long sputtering time. This saturation shows that the surface reaches an equilibrium state between the sputtered atoms and implanted ions. Moreover, the intensities of the reduced states increase with increasing accelerating voltage of the primary ions. The alteration by 10 V ion bombardment suggests that there is a critical energy for reduction to the Ti2+ state. Copyright © 2002 John Wiley & Sons, Ltd.
Oxidation of magnesium
Authors: Fournier V. , Marcus P. , Olefjord I.
Published: October 2002

Pure Mg was oxidized in 20 kPa O2, at temperatures between room temperature and 400°C, for times ranging from 2 min to 60 h. The oxide layer was analysed by XPS. The samples were pre‐treated by mechanical polishing and ion etching. Oxidation was carried out in a furnace connected to the XPS instrument. Magnesium was also oxidized in CO2 at 150°C and in water in order to gain information about the binding energies of the elements in MgCO3 and Mg(OH)2. The binding energies of Mg 2p, O 1s and C 1s of these compounds, as well as MgO, are reported. The thickness of the oxides formed during oxidation for 15 min at room temperature and at 150°C are 1.5 and 1.7 nm, respectively. At 300°C the growth of the oxide is well fitted by an inverse logarithmic law. The fact that the oxide formed in a dry atmosphere up to 300°C is extremely thin indicates that it has a low defect density. The influence of the humidity on the corrosion properties of Mg is discussed. The influence of the high vapour pressure of Mg on its oxidation properties is also mentioned. Copyright © 2002 John Wiley & Sons, Ltd.
High‐resolution XPS study of crosslinking and segregation phenomena in hexamethoxymethyl melamine–polyester resins
Authors: Perruchot Christian , Abel Marie‐Laure , Watts John F. , Lowe Chris , Maxted James T. , White Richard G.
Published: October 2002

Thermally initiated reactions that occur between a polyester resin and a hexamethoxymethyl melamine crosslinker, together with the segregation phenomenon of minor components such as flow agents, have been investigated by high‐resolution XPS. High‐resolution monochromated XPS C 1s spectra can be peak‐fitted by taking into account all functionalities of the respective components of the formulation. Uncured and cured coatings based on a mixture of hexamethoxymethyl melamine and a polyester resin exhibit minor differences in terms of surface composition and in the high‐resolution C 1s peak fitting. Examination of both the elemental and chemical surface compositions clearly demonstrates that the use of flow agents in the formulation leads to their preferential segregation towards the air/film interface. Copyright © 2002 John Wiley & Sons, Ltd.
Surface property modification of a polyethylene powder by coupling fluidized bed and far cold remote nitrogen plasma technologies
Authors: Vivien C. , Wartelle C. , Mutel B. , Grimblot J.
Published: October 2002

A far cold remote nitrogen (FCRN) plasma, eventually doped with oxygen, was used to modify the surface properties of a polyethylene (PE) powder. The process associates both remote plasma and fluidized bed technologies. Two applications are described. The first one, for increasing the hydrophilic character of PE, only requires a single plasma treatment. The second application involves FCRN plasma polymerization of 1,1,3,3‐tetramethyldisiloxane mixed with oxygen to obtain a hydrophobic film on the powder surface. The wettability evolution of the PE powder was followed by contact angle measurements (Washburn method) versus different experimental parameters. The surface modifications induced by the treatments were studied by XPS. Copyright © 2002 John Wiley & Sons, Ltd.
Formation of cubic boron nitride films by r.f. magnetron sputtering
Authors: Jiang Liudi , Fitzgerald A. G. , Rose M. J. , Lousa A. , Gimeno S.
Published: October 2002

Boron nitride thin films have been deposited on silicon by tuned substrate r.f. magnetron sputtering from a sintered hexagonal BN target using a mixture of Ar (90%) and N2 (10%) as sputtering gas at different substrate bias conditions. The deposited films have been characterized by Fourier transform infrared spectroscopy (FTIR) and x‐ray photoelectron spectroscopy (XPS). Both FTIR and XPS results show that the formation of nearly pure cubic boron nitride films were achieved when the films were deposited by a two‐step process at a lower substrate bias voltage after the initial formation of the cubic boron nitride layer. Also, as indicated by FTIR measurements, this two‐step process caused a reduction of the residual stress in the deposited films and no re‐sputtering effects were present during the cubic BN growing process. Copyright © 2002 John Wiley & Sons, Ltd.
Performance of weighted estimating equations for longitudinal binary data with drop‐outs missing at random
Authors: Preisser John S. , Lohman Kurt K. , Rathouz Paul J.
Published: October 2002

The generalized estimating equations (GEE) approach is commonly used to model incomplete longitudinal binary data. When drop‐outs are missing at random through dependence on observed responses (MAR), GEE may give biased parameter estimates in the model for the marginal means. A weighted estimating equations approach gives consistent estimation under MAR when the drop‐out mechanism is correctly specified. In this approach, observations or person‐visits are weighted inversely proportional to their probability of being observed. Using a simulation study, we compare the performance of unweighted and weighted GEE in models for time‐specific means of a repeated binary response with MAR drop‐outs. Weighted GEE resulted in smaller finite sample bias than GEE. However, when the drop‐out model was misspecified, weighted GEE sometimes performed worse than GEE. Weighted GEE with observation‐level weights gave more efficient estimates than a weighted GEE procedure with cluster‐level weights. Copyright © 2002 John Wiley & Sons, Ltd.
Ethical issues in clinical trials in developing countries
Authors: Brody Baruch A.
Published: October 2002

The vertical transmission trials conducted in a variety of developing countries by researchers from more developed countries illustrate a variety of crucial ethical issues. Three crucial issues are the injustice of the use of placebo control groups, the coerciveness of the offer to participate, and the exploitation of Third World countries. This paper examines each of these issues separately. It develops a new standard for when such control groups are acceptable. It concludes that the issue of coercive offers is not well founded. It also concludes that concerns about exploitation are better addressed by assurances about the future care of the subjects in the trial than by assurances of availability of the drugs in the country in general. Copyright © 2002 John Wiley & Sons, Ltd.
Combined endpoints: can we use them?
Authors: Lubsen Jacobus , Kirwan Bridget‐Anne
Published: October 2002

Analysing specific non‐fatal events in isolation may lead to spurious conclusions about efficacy unless the events considered are combined with all‐cause mortality. The use of combined endpoints has therefore become widespread, at least in cardiovascular disease trials. Combining all‐cause mortality with selected non‐fatal events is useful because event‐free survival, an important criterion in therapy evaluation, is addressed in this manner. In many clinical trials, symptoms, signs or paraclinical measures (for example, blood pressure, exercise duration, quality of life scores) are used as endpoints. If the patient died before the endpoint was measured, or it was otherwise not possible to perform follow‐up assessments as planned, the effect of treatment on these endpoints may be distorted if the patients concerned are ignored in the analysis. Examples are given of how distortion can be avoided by including all patients randomized in an analysis that uses a ranked combined endpoint based both on clinical events and on paraclinical measures. A distinction is made between a pseudo intention‐to‐treat analysis that disregards study medication status at the time of endpoint assessment but is confined to patients with data, and a true intention‐to‐treat analysis that takes into account all patients randomized based on a ranked combined endpoint. Copyright © 2002 John Wiley & Sons, Ltd.
Sense of personal control, stress and coping style: a cross‐cultural study
Authors: O'Connor Daryl B. , Shimizu Mikiko
Published: October 2002

The relationship between personal control, stress, and psychological health is well documented, but these associations may represent a Western bias—a sense of personal control may only reflect individualistic Western values—distinct from Eastern collectivist values. This study examined the relationship between sense of personal control, stress, coping and psychological distress in a Japanese and British sample. Japanese respondents were found to have a significantly lower sense of personal control, report higher perceived stress and negative mood compared to British respondents. Cultural differences in coping styles were also identified: Japanese respondents were found to employ significantly more emotion‐focused strategies (i.e. escape–avoidance and positive reappraisal) when faced with stressful encounters compared to the British sample. No differences were found for problem‐focused coping. Sense of personal control was only associated with stress, psychological distress and coping style in the British sample—providing support for the notion of a Western bias. The results are discussed within the context of cross‐cultural stress and coping research and implications for future investigations are discussed. Copyright © 2002 John Wiley & Sons, Ltd.
Is low cortisol release an indicator of positive health?
Authors: Lindfors Petra , Lundberg Ulf
Published: October 2002

Compared to the knowledge of physiological processes associated with stress, ill‐health, and disease, the understanding of physiological processes associated with positive psychological functioning is lagging behind. The present study aimed to examine the relationships between psychological well‐being and physiological indicators, including blood pressure, catecholamines, and cortisol. Initial questionnaires concerning demographic information, work characteristics (decision authority, job demands, and skill discretion), physical symptoms, nicotine use, and Ryff's Psychological Well‐Being scales (RPWB) which cover self‐acceptance, environmental mastery, positive relations with others, personal growth, purpose in life and autonomy, were completed by a group of highly educated white‐collar workers. Subsequent assessments of blood pressure, urinary catecholamines, and salivary cortisol were performed during two separate workdays. Analyses of data from 12 women and 11 men revealed that individuals with high psychological well‐being had significantly lower total cortisol output than individuals with low psychological well‐being (p < 0.01), while no significant differences emerged for blood pressure and catecholamines. Further, individuals with high psychological well‐being had significantly lower levels of general (p < 0.01) as well as musculoskeletal symptoms (p < 0.01). In conclusion, the findings suggest a link between positive psychological functioning and lowered cortisol release. Copyright © 2002 John Wiley & Sons, Ltd.
September 11, 2001
Authors: Wilkinson Christine K.
Published: October 2002

The September 11 terrorist attacks in the United States had an impact on everyone across the nation, and certainly included college campuses. This chapter addresses campus responses targeted at students and identifies future implications.
Acute and delayed effects of phencyclidine upon mRNA levels of markers of glutamatergic and GABAergic neurotransmitter function in the rat brain
Authors: Cochran Susan M. , Fujimura Masatake , Morris Brian J. , Pratt Judith A.
Published: October 2002

Glutamatergic and GABAergic neurotransmitter systems exist in equilibrium to maintain “normal” brain function. Evidence is accumulating that disturbance of this equilibrium may be one of the key factors giving rise to schizophrenia. While there is widespread evidence that the psychotomimetic phencyclidine (PCP) induces schizophrenia‐related symptoms, it is not clear how this dramatic effect is mediated. This study was designed to investigate acute and delayed effects of PCP on the mRNA expression of a range of markers of neuronal function associated with the glutamatergic and GABAergic systems within the rat brain. The mRNA levels of CaMKIIα, an enzyme which is located within the postsynaptic density and phosphorylates AMPA receptors, remained unaltered both 2 and 24 h posttreatment. Homer 1a, an immediate early gene associated with metabotropic glutamate receptors within the postsynaptic density, displayed region‐specific differential changes within the prefrontal, primary auditory, and retrosplenial cortices 2 and 24 h posttreatment. Parvalbumin, a calcium‐binding protein located within a subpopulation of GABAergic interneurones, displayed altered mRNA levels within the reticular nucleus of the thalamus at 2 and 24 h posttreatment and the substantia nigra pars reticulata 24 h posttreatment only. These phencyclidine‐induced changes in mRNA expression were not accompanied by any changes in hsp‐70 mRNA levels, a marker of NMDA antagonist‐induced reversible neurotoxicity. These results indicate that the glutamatergic (group I metabotropic glutamate receptors) and GABAergic (parvalbumin‐containing interneurones) neurotransmitter systems are differentially modulated in a region‐ and time‐dependent manner by exposure to phencyclidine. Synapse 46:206–214, 2002. © 2002 Wiley‐Liss, Inc.
Formulating measures of effectiveness
Authors: Sproles Noel
Published: October 2002

Although Measures of Effectiveness (MOEs) are an important element of the Systems Engineering process, they have yet to gain acceptance from practitioners. This is caused not only by the confusion surrounding their definition but also the perceived difficulty in formulating appropriate MOEs. This paper builds on previously published papers that address the issue of the definition of MOEs and the distinction to be drawn with Measures of Performance. Following a brief review of this existing work, a process for formulating MOEs is suggested and explained. This is supplemented by several examples from everyday life and from historical references. The examples build on the issues raised in the discussion of the process and provide practical examples to reinforce what has been previously discussed. © 2002 Commonwealth of Australia. Exclusive worldwide publication rights in the article have been transferred to Wiley Periodicals, Inc. Syst Eng 5, 253–263, 2002
Biologically Important Reactions Catalyzed by RNA Molecules
Authors: Ikeda Yutaka , Taira Kazunari
Published: October 2002

The last few years have seen a considerable increase in our understanding of catalysis by naturally occurring RNA molecules called ribozymes. The biological functions of RNA molecules depend upon their adoption of appropriate three‐dimensional structures. The structure of RNA has a very important electrostatic component, which results from the presence of charged phosphodiester bonds. Metal ions are usually required to stabilize the folded structures and/or catalysis. Some ribozymes utilize metal ions as catalysts, whereas others use the ions to maintain appropriate three‐dimensional structures. In the latter case, the correct folding of the RNA structures can perturb the pKa values of the nucleotide(s) within a catalytic pocket such that they act as general acid/bases catalysts. © 2002 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 2: 307–318, 2002: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10031