bluuebunny/crossref_metadata_2025 huggingface dataset:
Dance of Decadence: Class, Gender, and Modernity in the Scherzo of Mahler's Ninth Symphony
Authors: Draughon Francesca Draughon
Published: March 2004

The Scherzo of Mahler's Ninth Symphony juxtaposes the Lndler and the waltz, two dances that resonate with cultural meaning. Exploring the part they play in this movement illuminates the socio-political significance of the dances' identification with contrasting-and at the turn of the century increasingly conflicted-social spheres of the Habsburg Empire: The former represented the rural population of the countryside, while the latter represented the bourgeois and aristocratic classes of Vienna. This rural-urban polarity was intimately bound with turn-of-the-century ideologies of gender, the body, and decadence. While the Stadtmensch's body came to be regarded as a potential carrier of a feminized, urban degeneracy, the ideology of Körperkultur (body culture) proposed a cure for this degeneracy in an idealized chaste and rural male body. Mahler's juxtaposition of the Ländler and waltz, when observed through this lens, creates a narrative of dangerous feminine seduction. Additionally, consideration of Mahler's own politicized body and his relationship to Körperkultur points to ways in which these two cultural discourses may have informed the popular "death" or "farewell" narrative commonly attributed to the Ninth Symphony.
Human Histologic Analysis of Mineralized Bone Allograft (Puros) Placement Before Implant Surgery
Authors: Minichetti John C. , D'Amore Joseph C. , Hong Anna Y. J. , Cleveland Deborah B.
Published: March 2004

Because clinicians are placing more dental implants, it is becoming more important to maintain bone volume after tooth extraction. This article discusses the various bone-augmentation materials available to the clinician and illustrates a case report of particulate mineralized bone allograft (Puros) placement after extraction. Exposure of the grafted site after 5 months revealed a hard bony structure. Human histologic analysis at the light microscopic level revealed nonvital spicules of mature calcified bone having a highly organized matrix surrounded by viable noncalcified immature bone matrix, or osteoid. It was concluded that mineralized human allograft demonstrated the formation or remodeling of bone histologically and was clinically useful to maintain bone volume for implant placement after extraction. To the authors' knowledge, this is the first publication to demonstrate human histology of particulate mineralized bone allograft (Puros) after placement into an extraction site.
President Bush's false [flashbulb] memory of 9/11/01
Authors: Greenberg Daniel L.
Published: March 2004

Many people claim to remember how they heard about the terrorist attacks of September 11, 2001—including George W. Bush, the President of the United States at the time. On at least three occasions, the President was asked how he heard the news of the attacks. His answers contained substantial inconsistencies and provide a near‐perfect example of a false flashbulb memory. Copyright © 2004 John Wiley & Sons, Ltd.
Rapid judgements in assessing verbal and nonverbal cues: their potential for deception researchers and lie detection
Authors: Vrij Aldert , Evans Hayley , Akehurst Lucy , Mann Samantha
Published: March 2004

In the present study it was investigated to what extent observers (i) could make rapid yet reliable and valid judgements of the frequency of verbal and nonverbal behaviours of interviewees (liars and truth tellers) and (ii) detect deceit after making these rapid judgements. Five observers watched 52 videoclips of 26 liars and 26 truth tellers. The findings revealed that rapid judgements were reliable and valid. They also revealed that observers were able to detect truths and lies well above the level of chance after making these rapid judgements (74% accuracy rate was found). The implications of these findings for deception researchers and lie detection are discussed. Copyright © 2004 John Wiley & Sons, Ltd.
The impact of cognitive test anxiety on text comprehension and recall in the absence of external evaluative pressure
Authors: Cassady Jerrell C.
Published: March 2004

Two studies examined the effects of cognitive test anxiety on students' memory, comprehension, and understanding of expository text passages in situations without externally‐imposed evaluative pressure. The results gathered through structural equations modelling demonstrated a significant impact of cognitive test anxiety on performance in conditions with and without external evaluative pressure. The impact of cognitive test anxiety was stronger in those conditions with external evaluative pressure. The results are interpreted to support processing models of test anxiety that propose test anxiety interferes with learning through deficiencies in encoding, organization, and storage in addition to the classic interpretation of retrieval failures. In addition, the data provide support for additive models of test anxiety that address both stable and situational factors in the overall impact of cognitive test anxiety on performance. Copyright © 2004 John Wiley & Sons, Ltd.
Minimising misinformation effects in young children with cognitive interview mnemonics
Authors: Holliday Robyn E. , Albon Amanda J.
Published: March 2004

This research evaluated the effect of several variations of a Cognitive interview on 4–5‐year‐old children's correct recall and subsequent reporting of misinformation. Children viewed an event followed by misinformation that was read or self‐generated before a Cognitive interview. Children were then given recognition tests under inclusion and exclusion instructions. Developmentally modified Cognitive interviews elicited significantly more correct details than control interviews. A Cognitive interview given after misinformation reduced children's reporting of misinformation at interview and reduced reporting of self‐generated misinformation on memory tests. Moreover, this research shows that thereport allandcontext reinstatementCognitive interview mnemonics in combination can offer some protection against the negative effect of misinformation when given after such misinformation. Process dissociation analyses revealed that both recollection and familiarity contributed to children's reporting of misinformation. Copyright © 2004 John Wiley & Sons, Ltd.
Attention and expertise in multiple target tracking
Authors: Allen Roy , Mcgeorge Peter , Pearson David , Milne Alan B.
Published: March 2004

An experiment is reported examining the role of attention and expertise in multiple target tracking. It compares the ability of professional radar operators (experts) and undergraduate students (novices) to acquire and track subsets of randomly moving targets amongst distractors, and respond appropriately to a probe. Participants undertook this tracking task alone then, subsequently, in conjunction with a second, digit categorization task. For half the participants, the second task commenced prior to the tracking task's target acquisition phase, for the remainder after. Results suggest experts are better than novices across all conditions. Further, a comparison of results between the two dual task conditions indicates that attentional resources make a contribution to target tracking in both novices and experts, but only appear to make a contribution to target acquisition in novices. The results have implications for theories of multiple target tracking; the selection of radar operators; and the monitoring of their training. Copyright © 2004 John Wiley & Sons, Ltd.
The effects of aging on a measure of prospective remembering using naturalistic stimuli
Authors: McDermott Kate , Knight Robert G.
Published: March 2004

The aim of this study was to determine the effect of age on the noticing and memory search stages of a prospective memory task. Three groups (n=30) of older, middle‐aged, and younger persons were compared on a task using naturalistic stimuli, designed to simulate prospective remembering in everyday life. Participants were given a list of 30 instructions, each comprising an action (e.g. [Buy a hamburger]) and associated cue (e.g. [At McDonalds]). They then watched a videotape showing the view a person would have walking along a city street and attempted to recall each task when the cue appeared. The key finding was that older participants had a disproportionate reduction in recall of actions relative to cues noticed compared to both younger and middle‐aged participants. Although the older group were significantly less likely to notice cues than were the younger participants, noticing was preserved relative to memory search. The implication of this is that noticing complex and naturalistic visual cues in a shopping environment may rely primarily on automatic memory processes, whereas memory search depends on more strategic and conscious memory processes. Copyright © 2004 John Wiley & Sons, Ltd.
Towards a performance theory of robust adaptive control
Authors: Sanei Ahmad , French Mark
Published: March 2004

We consider standard robust adaptive control designs based on the dead‐zone and projection modifications, and compare their performance w.r.t. a worst case transient cost functional penalizing theℒ︁∞norm of the output, control and control derivative. If a bound on theℒ︁∞norm of the disturbance is known, it is shown that the dead‐zone controller outperforms the projection controller if thea prioriinformation on the uncertainty level is sufficiently conservative. The second result shows that the projection controller is superior to the dead‐zone controller when thea prioriinformation on the disturbance level is sufficiently conservative. For conceptual clarity the results are presented on a non‐linear scalar system with a single uncertain parameter and generalizations are briefly discussed. Copyright © 2004 John Wiley & Sons, Ltd.
Biocatalytic Potential of p‐Hydroxybenzoate Hydroxylase from Rhodococcus rhodnii 135 and Rhodococcus opacus 557
Authors: Jadan Andrei P. , Moonen Mariëlle J. H. , Boeren Sjef , Golovleva Ludmila A. , Rietjens Ivonne M. C. M. , van Berkel Willem J. H.
Published: March 2004

The biocatalytic potential of the NADH‐dependent p‐hydroxybenzoate hydroxylases (PHBH) from Rhodococcus rhodnii 135 and Rhodococcus opacus 557 was investigated. Monofluorinated 4‐hydroxybenzoates were efficiently hydroxylated, albeit at different rates. 2‐Fluoro‐4‐hydroxybenzoate was a true substrate for PHBH from R. rhodnii 135 but a substrate inhibitor for PHBH from R. opacus 557. Monochlorinated 4‐hydroxybenzoates also acted as PHBH substrates, but with these compounds strong uncoupling of hydroxylation (formation of hydrogen peroxide) occurred. PHBH from R. rhodnii 135 preferred the 5′‐hydroxylation of 2‐chloro‐4‐hydroxybenzoate but the enzyme from R. opacus 557 favored the formation of 2‐chloro‐3,4‐dihydroxybenzoate. Conversely, PHBH from R. rhodnii 135 regioselectively hydroxylated 2‐fluoro‐4‐hydroxybenzoate to 2‐fluoro‐3,4‐dihydroxybenzoate whereas the enzyme from R. opacus 557 also produced significant amounts of 2‐fluoro‐4,5‐dihydroxybenzoate. At high NADH/substrate ratio, both 2‐fluorodihydroxybenzoate products were further converted to 2‐fluoro‐3,4,5‐trihydroxybenzoate. PHBH from R. rhodnii 135 and R. opacus 557 preferred the 5′‐hydroxylation of 3‐chloro‐4‐hydroxybenzoate. However, conversion of 3‐fluoro‐4‐hydroxybenzoate involved considerable dehalogenation affording nearly equal amounts of 3,4‐dihydroxybenzoate and 5‐fluoro‐3,4‐dihydroxybenzoate. At high NADH/substrate ratio, the latter compound was further converted to 3,4,5‐trihydroxybenzoate. The results are discussed in relation to the properties of the NADPH‐specific PHBH from Pseudomonas fluorescens.
Expedient Synthesis of 4‐Dialkylamino‐5H‐furan‐2‐ones by One‐Pot Sequential Pd‐Catalyzed Oxidative Carbonylation of 2‐Yn‐1‐ols–Conjugate Addition‐Lactonization
Authors: Gabriele Bartolo , Salerno Giuseppe , Plastina Pierluigi , Costa Mirco , Crispini Alessandra
Published: March 2004

A novel synthesis of 4‐dialkylamino‐5H‐furan‐2‐ones 3 starting from very simple building blocks, i.e., α‐substituted 2‐yn‐1‐ols 1, carbon monoxide, dialkylamines 2 and oxygen is reported. Reactions are carried out in 1,2‐dimethoxyethane at 100 °C and under 20 atm (at 25 °C) of a 4/1 mixture of CO/air in the presence of catalytic amounts of PdI2 in conjunction with 10 equiv. of KI. Formation of 3 occurs through an ordered sequence of steps, namely (a) Pd‐catalyzed oxidative monoaminocarbonylation of 1 to give 4‐hydroxy‐2‐ynamides 4, which can be isolated under appropriate conditions; (b) stereoselective conjugate addition of 2 to the triple bond of 4, with formation of (not isolated) (E)‐3‐dialkylamino‐4‐hydroxy‐2‐enamides; (c) intramolecular alcoholysis of the amide function of the latter to give the final product 3.
Liquid Phase Oxidation of Alkenes with Nitrous Oxide to Carbonyl Compounds
Authors: Starokon E. V. , Dubkov K. A. , Babushkin D. E. , Parmon V. N. , Panov G. I.
Published: March 2004

A variety of substrates including linear, cyclic, heterocyclic alkenes and their derivatives were tested in the liquid phase non‐catalytic oxidation with nitrous oxide (N2O). The structure and composition of the alkenes have a significant effect on the reaction selectivity. With many alkenes, N2O oxidation provides a selective way for the preparation of carbonyl compounds. The generation of carbene (or diazomethane) species is a remarkable feature of the oxidation of terminal alkenes.
Aqueous Biphasic Oxidation: A Water‐Soluble Polyoxometalate Catalyst for Selective Oxidation of Various Functional Groups with Hydrogen Peroxide
Authors: Sloboda‐Rozner Dorit , Witte Peter , Alsters Paul L. , Neumann Ronny
Published: March 2004

A “sandwich” type polyoxometalate, Na12[(WZn3(H2O)2][(ZnW9O34)2], was used as an oxidation catalyst in aqueous biphasic reaction media to effect oxidation of alcohols, diols, pyridine derivatives, amines and aniline derivatives with hydrogen peroxide. The catalyst was shown by 183W NMR to be stable in aqueous solutions in the presence of H2O2 and showed only minimal non‐productive decomposition of the oxidant. Secondary alcohols were selectively oxidized to ketones, while primary alcohols tended to be oxidized to the corresponding carboxylic acids, although secondary alcohols were selectively oxidized in the presence of primary alcohols. Vicinal diols yielded carbon‐carbon bond cleavage products in very high yields. Pyridine derivatives were oxidized to the respective N‐oxides, but strongly electron‐withdrawing moieties inhibited the oxidation reaction. Primary amines were oxidized to the oximes, but significantly hydrolyzed in situ. Aniline derivatives were oxidized to the corresponding azoxy or nitro products depending on the substitution pattern in the aromatic ring. Catalyst recovery and recycle was demonstrated.
Application of High Throughput Screening to Heterogeneous Liquid and Gas Phase Oxidation Catalysis
Authors: Guram Anil , Hagemeyer Alfred , Lugmair Claus G. , Turner Howard W. , Volpe Anthony F. , Weinberg W. Henry , Yaccato Karin
Published: March 2004

The application of combinatorial methods to oxidation catalysis in the liquid and gas phases is described. New lead materials have been discovered for the selective liquid phase oxidation of alcohols to aldehydes/ketones catalyzed by vanadium supported on carbon, for the low temperature CO oxidation/light off for cold start automotive emissions control over supported noble metals and perovskites, for volatile organic compound (VOC) removal using CoCr oxide catalysts, and for the selective gas phase oxidation of propane to acrylic acid and acrylonitrile using mixed metal oxides. Catalyst discovery libraries were screened in 96‐well batch reactors, in a rapid serial scanning mass spectrometer and in a massively parallel microfluidic reactor as primary screens. Promising hits were scaled up in conventional autoclaves or in multi‐channel fixed bed secondary/tertiary screening reactors.
Catalytic Aerobic Generation of Acyliminium Ions through Electron‐Transfer‐Mediated Carbon‐Carbon Bond Activation
Authors: Aubele Danielle L. , Rech Jason C. , Floreancig Paul E.
Published: March 2004

Homobenzylic amides and carbamates, upon single‐electron oxidation, undergo mesolytic cleavage reactions to form acyliminium ions. Appending nucleophilic groups to these substrates results in cyclization reactions to form N‐acylaminals. The N‐methylquinolinium ion that serves as the photooxidant in these reactions can function as a catalyst when dioxygen is introduced into these reactions, representing a unique method for effecting catalytic, aerobic oxidations. Herein we present a full account of our studies on catalytic aerobic electron‐transfer‐initiated cyclization reactions of homobenzylic amides and carbamates, with particular emphasis on the roles of the amide group, the nucleophilic group, and the functionality in the tether in promoting efficient ring constructions and altering reaction mechanisms.
Cyclohexene and Cyclooctene Epoxidation with Aqueous Hydrogen Peroxide using Transition Metal‐Free Sol‐Gel Alumina as Catalyst
Authors: Rinaldi Roberto , Sepúlveda Jorge , Schuchardt Ulf
Published: March 2004

It is shown that sol‐gel alumina calcined at 400 0C is a very efficient catalyst for the epoxidation of cyclohexene and cyclooctene with aqueous 70 wt % hydrogen peroxide. The overall yield per g of catalyst was 0.28 mol of cyclohexene oxide in 5 cycles of 450 min each and 0.43 mol of cyclooctene oxide in 4 cycles of 750 min each. The selectivity for the epoxides was always better than 99%. However, the catalyst deactives slowly, which we believe is caused by a non‐radical decomposition of hydrogen peroxide.
Titanium Silicalite 1 (TS‐1) Catalyzed Oxidative Transformations of Furan Derivatives with Hydrogen Peroxide
Authors: Wahlen Joos , Moens Bart , De Vos Dirk E. , Alsters Paul L. , Jacobs Pierre A.
Published: March 2004

The oxidation of furan derivatives with titanium silicalite 1 (TS‐1) and hydrogen peroxide is described. Oxidation products are identified and possible reaction pathways are discussed. It is shown that the oxidation of these compounds occursviaepoxidation of one of the furan double bonds. The initially formed epoxides immediately undergo rearrangement, furans yielding unsaturated 1,4‐dicarbonyl compounds and furfuryl alcohols yielding 6‐hydroxy‐2H‐pyran‐3(6H)‐ones. The latter compounds originate from cyclization of intermediate enedione alcohols. The presented method is particularly useful for the oxidation of 2,5‐dimethylfuran to 3‐hexene‐2,5‐dione and the conversion of furfuryl alcohol to 6‐hydroxy‐2H‐pyran‐3(6H)‐one, a versatile synthon in organic synthesis.
The Resolution of Important Pharmaceutical Building Blocks by Palladium‐Catalyzed Aerobic Oxidation of Secondary Alcohols
Authors: Caspi Daniel D. , Ebner David C. , Bagdanoff Jeffrey T. , Stoltz Brian M.
Published: March 2004

The palladium‐catalyzed aerobic oxidative kinetic resolution of key pharmaceutical building blocks is described. Substrates investigated are relevant to the enantioselective preparation of Prozac®, Singulair®, and the promising hNK‐1 receptor antagonist from Merck. The latter provides the most selective aerobic oxidative kinetic resolution yet described.
IBX‐Mediated Conversion of Primary Alcohols and Aldehydes to N‐Hydroxysuccinimide Esters
Authors: Schulze Agnes , Giannis Athanassios
Published: March 2004

Recently, the use of the hypervalent iodine reagent 1‐hydroxy‐1,2‐benziodoxol‐3(1H)‐one 1‐oxide (IBX) for the oxidation of primary alcohols and aldehydes to carboxylic acids was described. During the synthesis of these carboxylic acids the corresponding N‐hydroxysuccinimide esters were formed as intermediate products, but their isolation as main reaction products was not successful. We report herein a simple and very efficient method to prepare these synthetically valuable active esters.
Hypervalent Iodine Reagents for the Oxidation of Alcohols and Their Application to Complex Molecule Synthesis
Authors: Tohma Hirofumi , Kita Yasuyuki
Published: March 2004

Hypervalent iodine(V) derivatives such as 2‐iodoxybenzoic acid (IBX) and Dess–Martin periodinane [DMP; 1,1,1‐tris(acetyloxy)‐1,1‐dihydro‐1,2‐benziodoxol‐3‐(1H)‐one] have been used widely for the oxidation of alcohols to aldehydes and ketones during the last decade because of their high chemoselectivity, mild reactivity, and high yielding process. This review focuses on the recent progress in the oxidation of alcohols to carbonyl compounds using IBX, DMP, and other hypervalent iodine reagents, and their application to total syntheses of a variety of complex natural products.
Is it Possible to Achieve Highly Selective Oxidations in Supercritical Water? Aerobic Oxidation of Methylaromatic Compounds
Authors: Garcia‐Verdugo Eduardo , Venardou Eleni , Thomas W. Barry , Whiston Keith , Partenheimer Walter , Hamley Paul A. , Poliakoff Martyn
Published: March 2004

We have demonstrated that different methylaromatic compounds [1,4‐dimethylbenzene (p‐xylene), 1,3‐dimethylbenzene (m‐xylene), 1,2‐dimethylbenzene (o‐xylene), 1,3,5‐trimethylbenzene (mesitylene) and 1,2,4‐trimethylbenzene (pseudocumene)] can be aerobically oxidized in supercritical water (scH2O) using manganese(II) bromide as catalyst to give corresponding carboxylic acids in the continuous mode over a sustained period of time in good yield. No partially oxidized intermediates (i.e., toluic acid and benzaldehydes) were detected for the dimethylbenzenes and mesitylene reactions. By fine tuning pressure and temperature, scH2O becomes a solvent with physical properties suitable for single‐phase oxidation since both organic substrate and oxygen are soluble in scH2O. There is a strong structural similarity of metal/bromide coordination compounds in the active oxidation solvents (acetic acid and scH2O) which does not exist in the much less active H2O at lower temperatures. This may account for the successful catalysis of the reactions reported herein. Aromatic acids produced by the loss of one methyl group occurred in all of these reactions, i.e., 3–6% benzoic acid formed during the oxidation of the dimethylbenzenes. Part of this loss is thought to be due to thermal decarboxylation. The thermal decarboxylation process is monitored via Raman spectroscopy.
A New Environmentally Benign Catalytic Process for the Asymmetric Synthesis of Lactones: Synthesis of the Flavouring δ‐Decalactone Molecule
Authors: Corma Avelino , Iborra Sara , Mifsud María , Renz Michael , Susarte Manuel
Published: March 2004

The system Sn‐Beta/hydrogen peroxide is applied to the Baeyer–Villiger oxidation of delfone to δ‐decalactone, which is an industrial fragrance. The reaction is carried out without solvent and with a substrate/catalyst ratio>200 (wt/wt). Starting with an enantiomerically enriched delfone it is shown that the rearrangement occurs with retention of configuration at the migrating asymmetric carbon atom, and enantiomerically enriched δ‐decalactone is obtained as product. This process offers clear advantages over the actual industrial production that uses peracids as oxidants.
Copolyesters of poly(butylene terephthalate), 1,4‐naphthalene dicarboxylic acid, and hydroquinone diacetate: A simple rate model
Authors: Bishara Ahmed , Al‐Adwani Hamad , Shaban Habib I.
Published: March 2004

The kinetics of novel liquid crystalline copolyesters between poly(butylene terephthalate) (PBT), 1,4‐naphthalene dicarboxylic acid (1,4 NDCA), and hydroquinone diacetate (HQDA) are examined by using the melt polymerization route. Three different copolyester compositions (i.e., PBT 70 mol % + 1,4 NDCA 15 mol % + HQDA 15 mol %, PBT 50 mol % + 1,4 NDCA 25 mol % + HQDA 25 mol %, and PBT 30 mol % + 1,4 NDCA 35 mol % + HQDA 35 mol %) were synthesized via the melt polymerization route. Sodium acetate and zinc acetate, 1.0 mol %, concentrations were tried as the polymerization catalysts. The reaction temperatures were 260, 270, and 280°C for PBT 70 and PBT 50 mol % compositions. PBT 30 mol % compositions were synthesized at 245, 255, and 265°C by using the above catalysts. Lower temperatures were employed for PBT 30 mol % reactions to avoid degradation reactions. The kinetics of complex systems are analyzed by methods analogous to solution kinetics. Few assumptions are proposed and tried to simplify the kinetics of this complex system and to make the kinetic analysis tractable. Two different models containing different rate constants, k1 and k2, are considered in this work. A key postulation is that the reaction originates between 1, 4 NDCA and HQDA to form a dimer. This dimer copolymerizes with the PBT chain with evolution of acetic acid (model 1) or without (model 2). The subsequent coupling of PBT segments reforms the PBT chain in the case of model 1 with random incorporation of 1, 4 NDCA–HQDA units; whereas blocks of PBT units and 1, 4 NDCA + HQDA units are formed in the case of model 2. The kinetic analysis reveals the implicit simplicity of complex systems. The number of moles of acetic acid, generated in both homopolyesterification and copolyesterfication channels, is monitored to follow the rate of the reaction and evaluate the individual rate constants. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2817–2832, 2004
Estimation of the oxygen‐limiting amount consumed by polymeric melt in the thermooxidative degradation process
Authors: Kozlov G. V. , Shustov G. B. , Zaikov G. E.
Published: March 2004

Fractal analysis representations were shown to elucidate quantitative relationships between the parameters of thermooxidative degradation and polymeric melt structure. The process of oxidative consumption during degradation was defined by both the polymer's chemical constitution and the structure of the macromolecular coil. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2840–2844, 2004
Functional barriers in PET recycled bottles. Part I. Determination of diffusion coefficients in bioriented PET with and without contact with food simulants
Authors: Pennarun P. Y. , Dole P. , Feigenbaum A.
Published: March 2004

A major outcome for recycled plastics consists of making food packaging materials. However, any contamination of collected plastics with chemicals may then be of concern for public health. A solution to mind migration is to use a layer of virgin polymer, named functional barrier, intercalated between the recycled layer and the food. This article aims to provide experimental values of diffusion coefficients (D) of model pollutants (surrogates) in poly(ethylene terephthalate) (PET) to be used for modeling migration through functional barriers. Diffusion coefficients of a large set of surrogates at low concentrations in PET were measured in various conditions. A solid‐to‐solid diffusion test was designed to avoid the use of a solvent that may induce plasticizing of the material and partitioning effects at the interface. Using [Log D = f(molecular weight)] correlations, the values of diffusion coefficients and activation energies of the surrogates measured by this method were shown to be consistent with the literature data obtained for gases, in permeation experiments, where no plasticization occurred. Migration from PET into food simulants was then studied. Migration into an aqueous medium is largely influenced by the solubility of the surrogates, the less soluble ones being not detected, despite high D values. With ethanol solvent, there were no partitioning effects, and the high plasticization effect of PET by ethanol considerably increases the apparent diffusion coefficients. The effects of temperature and plasticization on the relationship between diffusion coefficients and molecular weight are discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2845–2858, 2004
Effects of compatibilization of oxidized polypropylene on PP blends of PP/PA6 and PP/talc
Authors: Abdouss Majid , Sanjani Naser Sharifi , Azizinejad Fariborz , Shabani Mohsen
Published: March 2004

The influence of compatibilization on the dynamic mechanical properties of polypropylene (PP) binary blends with polyamide‐6 (PA6), Talc, and oxidized PP (OPP) was investigated. The oxidation of PP homopolymer was performed in a internal mixer by using air as a oxidizing agent (under atmospheric pressure) and dodecanol‐1 as an accelerator at 180°C for 6½ h [Abdouss, M.; Sharifi‐Sanjani, N.; Bataille, P. J Appl Polym Sci 1999, 36, 10]. In the blends, OPP was used as a blend component and compared with PP over the whole concentration range. Pressed film blends of PP/OPP, PP/OPP/Talc, and PP/OPP/PA6 were examined by dynamic mechanical analyzer, thermal gravimetry analysis, and scanning electron microscopy. Mechanical properties such as tensile strength, modulus of elasticity, elongation, melt flow index, and hardness of the blends were measured. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2871–2883, 2004
Kaolin modified with new resin–iron chelate as flame retardant system for polypropylene
Authors: Shehata A. B. , Hassan M. A. , Darwish N. A.
Published: March 2004

Polypropylene's fire‐retardant properties can be improved by using modified kaolin. Modification was done by reaction of kaolin with a prepared resin–iron chelate. Polypropylene samples were loaded with different amounts of kaolin, modified kaolin, and their mixture. Ignition properties of the produced samples were evaluated using cone calorimeter, UL 94, and thermogravimetric analysis techniques. It was found that sample S2 loaded with a mixture of kaolin and modified kaolin had significantly reduced the smoke generation and had a heat release rate comparable to that with kaolin. It was also found that samples S4 and S5 loaded with modified kaolin burned out earlier than did the other samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3119–3125, 2004
Multienzyme‐immobilized modified polypropylene membrane for an amperometric creatinine biosensor
Authors: Hsiue Ging‐Ho , Lu Pei‐Lin , Chen Jyh‐Chern
Published: March 2004

Creatinine has become an important clinical analyte that is used for the determination of renal and muscular dysfunction. It is essential to determine its concentration in the serum of patients suffering from renal insufficiency. Therefore, an amperometric creatinine biosensor fabricated from a covered platinum/silver electrode with a thin layer of an immobilized multienzyme membrane was studied. Poly(acrylic acid) was introduced onto an argon‐plasma‐treated porous polypropylene membrane surface by graft copolymerization. Subsequently, three different enzymes (sarcosine oxidase, creatinase, and creatininase) were immobilized onto this novel grafted membrane simultaneously via a carbodiimine agent to form a thin layer. The sensor performance was evaluated with a biochemistry analyzer. Moreover, attenuated total reflection/Fourier transform infrared, electron spectroscopy for chemical analysis, and scanning electron microscopy were used to confirm the progression of these reactions. The developed sensor showed a linear detection range of 3.2–320 μM for creatinine in a pH 7.4 buffered solution with 0.1M phosphate. The immobilized multienzyme membrane could be used for at least 3 weeks. The results obtained in our study will hopefully lead to the successful application of modified polypropylene for the development of a creatinine sensor. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3126–3134, 2004
Trace metal ion retention properties of crosslinked poly(4‐vinylpyridine) and poly(acrylic acid)
Authors: Rivas Bernabé L. , Quilodrán Benita , Quiroz Eduardo
Published: March 2004

The crosslinked resins poly(4‐vinylpiridine) (PVPy) and poly(acrylic acid) (PAA) were obtained by radical polymerization. PVPy shows monodentate ligands and PAA at basic pH is basically as acrylate anion, which can contain end‐carboxylates groups or form a bridge acting as mono‐ or bidentate ligands. The retention properties for trace metal ions from saline aqueous solutions and natural seawaters of these two resins were investigated by Batch equilibrium procedure. The metal ions studied were Cu(II), Pb(II), Cd(II), and Ni(II). The following effects were studied: pH, contact time, amount of the adsorbent, temperature, and salinity. The resin PVPy showed a high affinity for Cd(II) and PAA for Cu(II) and Cd(II). The metal ions were determined in the filtrate by atomic absorption spectrometry. By the treatment of the loaded resin with 4M HNO3, it was possible to remove completely the Cu(II) ions. The retention properties of the resins were studied for trace metal ions present in the natural seawaters. Both resins showed a high affinity for Cd(II) when the natural seawater contained Cu(II) and Cd(II). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2908–2916, 2004
Metal ion binding capability of the water‐soluble poly(vinyl phosphonic acid) for mono‐, di‐, and trivalent cations
Authors: Rivas Bernabé L. , Pereira Eduardo , Gallegos Paola , Homper Daniela , Geckeler Kurt E.
Published: March 2004

A water‐soluble polymer containing phosphonic acid groups was investigated as a polychelatogen by using the liquid‐phase polymer‐based retention technique (LPR) under different experimental conditions. The maximum retention capacity of this polymer was determined at different pHs and polymer–metal ion ratios. The metal ions investigated were Ag(I), Cu(II), Co(II), Ni(II), and Cr(III). The maximum retention capacity values of the divalent metal ions were very similar and higher than those for the trivalent cations, indicating that the polymer–metal ion interaction was basically through electrostatic type. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2917–2922, 2004
Fabrication of three‐dimensionally ordered microporous membrane by wet phase separation
Authors: Taketani Yuko , Nagaoka Shoji , Kawakami Hiroyoshi
Published: March 2004

We report a novel porous fluorinated polyimide membrane with a cylinder structure fabricated by a wet phase inversion process, which is formed by a ternary system, polyimide/solvent/water. The porous polyimide membranes consisted of a thin top porous layer and three‐dimensionally ordered cylinder micropores. The porous membrane‐forming solvents were N‐methylpyrrolidone containing nonsolvent additives such as alcohol, and the height and width of the cylinder structure were controlled by the solvents. Water fluxes through the porous polyimide membranes were measured using a stirred dead‐end filtration cell, and the fluxes of the porous membrane with the cylinder‐type structure were approximately three times greater than those of the membrane with the finger‐type structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3016–3021, 2004
Swelling behavior of chitosan/poly(acrylic acid) complex
Authors: Nge Thi Thi , Hori Naruhito , Takemura Akio , Ono Hirokuni
Published: March 2004

This study investigates the improved swelling behavior of chitosan/poly(acrylic acid) complex by solvent (methanol, ethanol, and acetone) extraction. The complex is developed by photoinitiated free‐radical polymerization of acrylic acid in the presence of chitosan. The swelling ratio of the complexes depends on the cosolvency effect of poly(acrylic acid) to the extracted solvent, which in turn affects the polymer network structure and ionic states characterized by dynamic force microscopy (DFM), Raman, and FT‐IR spectroscopy. The DFM investigation displays the improved structural changes of the polymer network structure after solvent extraction and its relation to the improved swelling property of the chosen system in different environmental conditions (pH, solvent, and salt concentration) are discussed. A high swelling ratio of about 600 times its dry weight is observed in water as well as in low salt and solvent concentration after methanol extraction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2930–2940, 2004
Synthesis and characterization of propylene‐α‐olefin random copolymers with isotactic propylene sequence. II. Propylene–hexene‐1 random copolymers
Authors: Shin Yong‐Woo , Hashiguchi Hideto , Terano Minoru , Nitta Koh‐hei
Published: March 2004

A series of novel hexene‐1–propylene random copolymers with isotactic sequence of propylene was synthesized with a MgCl2‐supported Cr(acac)3 catalyst. The molecular weight distribution of copolymers and homopolymers was considerably narrower than that of typical polyolefins produced by heterogeneous Ziegler–Natta catalysts. The crystallizability of the copolymers having a propylene‐unit content of more than 50 mol % drastically decreased with decreasing propylene‐unit content, and the copolymers with a propylene content of less than 50 mol % were completely amorphous. In the present novel type of random copolymers with crystallizable and noncrystallizable units, a single glass transition was observed between pure polypropylene and polyhexene‐1, and a major component was found to govern the final morphology and the mechanical characteristics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2949–2954, 2004
Influence of diblock copolymer on the morphology and properties of polystyrene/poly(dimethylsiloxane) blends
Authors: Chuai Chengzhi , Li Shu , Almdal Kristoffer , Alstrup Jan , Lyngaae‐Jørgensen Jørgen
Published: March 2004

Blends of polystyrene (PS) and poly(dimethylsiloxane) (PDMS), with and without diblock copolymers (PS‐b‐PDMS), were prepared by melt mixing. The melt rheology behavior of the blends was studied with a capillary rheometer. The morphology of the blends was examined with scanning electron microscopy. The miscibility of the blends was studied with differential scanning calorimetry. The morphology of PS/PDMS blends was modified by the addition of PS‐b‐PDMS copolymers and investigated as a function of the molar mass of the diblock copolymers, viscosity ratios and the processing conditions. As investigated, the observed morphology of the melt‐blended PS/PDMS pair unambiguously supported the interfacial activity of the diblock copolymers. When a few percent of the diblock copolymers blended together with the PS and PDMS homopolymers, the phase size was reduced and the phase dispersion was firmly stabilized against coalescence. The compatibilizing efficiency of the copolymers was strongly dependent on its molar mass. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2747–2757, 2004
Simple method of related sensitivity range to predict the thermodynamic equilibrium morphology of a core–shell latex particle
Authors: Zhao Ke , Sun Peiqin , Liu Dazhuang , Wang Lijun
Published: March 2004

The equilibrium morphologies of different core–shell latices are predicted, and a related sensitivity analysis is given for the predictions. This article proposes a related sensitivity range for estimating the accuracy of predictions, made with the simple method, of the thermodynamically preferred morphology of a core–shell latex particle in two‐stage seeded emulsion polymerization. The related sensitivity range of the predictions is defined and calculated, and the results show that different core–shell latices have different sensitivity ranges. The wider the sensitivity range is, the more reliable the prediction is of the morphology of the core–shell latex. The simple method of related sensitivity range has been verified in the literature and with experiments. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3144–3152, 2004
1,2‐propanediol–cellulose–acrylamide graft copolymers
Authors: Onishi Yasuhiko , Butler George B. , Hogen‐Esch Thieo E.
Published: March 2004

1,2‐Propanediol–cellulose–acrylamide graft copolymers (PCACs) were developed for enhanced oil recovery. They were prepared with acrylamide and 1,2‐propanediol (PDO)–cellulose, which was formed through the addition of glycols to cellulose by the Shotten–Baumann reaction between 3‐chloro‐1,2‐propanediol and cellulose. The graft copolymerization was initiated with a redox system between Ce4+ and glycols in cellulose. The infrared spectrum of PDO–cellulose had some characteristic absorption bands around 2960 (νCH) and 1050 cm−1 (νCO) that also appeared for the PDO group and pyranose ring of cellulose, respectively. The rate of Ce4+ consumption by PDO–cellulose was investigated through the calculation of the overall kinetic constant from the slopes of ln(D − DR) versus time (where D is the absorbance and DR is the absorbance of the original polysaccharide solution) The results showed that PDO–cellulose had high reactivity and that there were two mechanisms of oxidation by Ce4+ with PDO–cellulose. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3022–3029, 2004
Synthesis of urethane oils from waste poly(ethylene terephthalate) bottles
Authors: Saravari O. , Vessabutr B. , Pimpan V.
Published: March 2004

Waste poly(ethylene terephthalate) (PET) bottles were glycolyzed by propylene glycol (PG) at a weight ratio of PET to PG of 37.5 : 62.5 using zinc acetate as a catalyst. The glycolyzed product, consisting of oligomeric diols with a number‐average molecular weight range of 458–844, was obtained. It was further reacted with soybean oil and toluene diisocyanate to obtain urethane oils at hydroxyl to isocyanate ratios from 1 : 1 to 1 : 0.7, with and without methanol acting as a blocking agent. All the synthesized urethane oils were yellowish, transparent, low‐viscosity liquids of low molecular weights. A lower diisocyanate content and the presence of a blocking agent resulted in higher viscosity, higher molecular weight, and shorter drying time. The films of all synthesized urethane oils exhibited good hardness and adhesion. They also showed excellent water and acid resistance but only fair alkali resistance. However, these prepared urethane oils had lower flexibility and poorer wear resistance compared to those of the commercial urethane oil. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3040–3045, 2004
Response of human chondrocytes on polymer surfaces with different micropore sizes for tissue‐engineered cartilage
Authors: Lee Sang Jin , Lee Young Moo , Han Chang Whan , Lee Hai Bang , Khang Gilson
Published: March 2004

Response of chondrocytes on polymer surfaces is important for applications of tissue‐engineered cartilage, and tissue engineering contains the interaction of cells on material surfaces. We examined the behavior of human chondrocytes cultured on polycarbonate (PC) membranes with different micropore sizes (0.2–8.0 μm in diameter). The adhesion and proliferation of chondrocytes were evaluated by measuring the number of attached cells after 1, 2, and 4 days of culture and morphological observations. It seems that the cell adhesion and proliferation were progressively inhibited, as the PC membranes had micropores with increasing size, probably due to surface discontinuities produced by track‐etched pores. On the PC membrane with smaller micropore sizes, the cells seemed to override these surface discontinuities. Phenotype of chondrocyte was assessed by Safranin‐O staining for anionic sulfated proteoglycans. Chondrocytes on the 8.0 μm‐diameter membrane surface proliferated, on 8 days, formed morphology of round shape, and expressed proteoglycans, because of limitation of spreading by the track‐etched micropores. They maintained their phenotype under conditions that support a round cell shape on the large pore diameter substrate, whereas chondrocyte phenotypes lost on the small pore diameter membranes. In conclusion, this study demonstrated that micropore sizes as well as pore‐to‐pore distance play an important role for adhesion, proliferation, and phenotype of human articular chondrocytes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2784–2790, 2004
Dynamic rheological properties of high‐density polyethylene/polystyrene blends extruded in the presence of ultrasonic oscillations
Authors: Chen Guangshun , Guo Shaoyun , Li Yuntao
Published: March 2004

The linear rheological properties of high‐density polyethylene (HDPE), polystyrene (PS), and HDPE/PS (80/20) blends were used to characterize their structural development during extrusion in the presence of ultrasonic oscillations. The master curves of the storage shear modulus (G′) and loss shear modulus (G″) at 200°C for HDPE, PS, and HDPE/PS (80/20) blends were constructed with time–temperature superposition, and their zero shear viscosity was determined from Cole–Cole plots of the out‐of‐phase viscous component of the dynamic complex viscosity (η″) versus the dynamic shear viscosity. The experimental results showed that ultrasonic oscillations during extrusion reduced G′ and G″ as well as the zero shear viscosity of HDPE and PS because of their mechanochemical degradation in the presence of ultrasonic oscillations; this was confirmed by molecular weight measurements. Ultrasonic oscillations increased the slopes of log G′ versus log G″ for HDPE and PS in the low‐frequency terminal zone because of the increase in their molecular weight distributions. The slopes of log G′ versus log G″ for HDPE/PS (80/20) blends and an emulsion model were used to characterize the ultrasonic enhancement of the compatibility of the blends. The results showed that ultrasonic oscillations could reduce the interfacial tension and enhance the compatibility of the blends, and this was consistent with our previous work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3153–3158, 2004
Combustion‐thermal‐sprayed recycled poly(ethylene terephthalate)
Authors: Branco José Roberto Tavares , Campos Sthener Rodrigues Vieira , Duarte Luciana Tavares , Lins Vanessa De Freitas Cunha
Published: March 2004

Thermal‐sprayed polymer coatings have been used as protection against corrosion and wear. In this study, poly(ethylene terephthalate) (PET) powder, which was obtained from postconsumer beverage bottles, was deposited on 1020 steel by low‐velocity flame‐spray technology. The chemical and structural changes in PET due to the thermal‐spray processing were investigated with Fourier transform infrared spectroscopy and X‐ray diffraction. Changes in tribological behavior were examined by pin‐on‐disk testing and three‐dimensional profilometry. The results show that coatings had the same functional groups as the PET beverage bottles. However, the degree of crystallinity was modified. These changes were rationalized in terms of possible structural modifications of the PET polymer. The study showed evidence that the pin‐on‐disk wear developed by an abrasion process through a ploughing mechanism, although a fatigue mechanism could not be disregarded. A low friction coefficient between PET and steel was confirmed. In the as‐sprayed condition, the PET coatings showed higher friction, likely because of a higher coarse debris production rate during the pin‐on‐disk testing. Heat treating the as‐sprayed coating to increase the amorphous PET content improved the sliding behavior by increasing wear resistance. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3159–3166, 2004
Analysis of low‐density polyethylene‐g‐poly(vinyl chloride) copolymers formed in poly(vinyl chloride)/low‐density polyethylene melt blends with gel permeation chromatography and solid‐state 13C‐NMR
Authors: Sombatsompop N. , Sungsanit K. , Thongpin C.
Published: March 2004

Gel permeation chromatography (GPC) and solid‐state 13C‐NMR techniques were used to analyze the structural changes of poly(vinyl chloride) (PVC) in blends of a low‐density polyethylene (LDPE) and PVC during melt blending. The GPC results showed that the weight‐average molecular weight (Mw) of PVC increased with LDPE content up to 13.0 wt % and then decreased at a LDPE content of 16.7 wt %, whereas the number‐average molecular weight remained unchanged for all of LDPE contents used. The 13C‐NMR results suggest that the increase in Mw was associated with the formation of a LDPE‐g‐PVC structure, resulting from a PVC and LDPE macroradical cross‐recombination reaction during melt blending. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3167–3172, 2004