bluuebunny/crossref_metadata_2025_split huggingface dataset:
Deconstructing a definition: Social maladjustment versus emotional disturbance and moving the EBD field forward
Authors: Merrell Kenneth W. , Walker Hill M. 
Published: October 2004

AbstractIn this article we discuss the definition of emotionally disturbed (ED) from the Individuals with Disabilities Education Act, with a specific focus on the clause contained in this definition, which is designed to exclude from special education services students who are considered to be socially maladjusted (SM). The history of the SM exclusionary clause and its impact is detailed herein. We argue that the federal ED definition, and especially its SM exclusionary clause, have both served to inhibit the progress of the behavior disorders subspecialty within the special education field, and have diverted energy and attention from more important aspects of serving students with behavioral and emotional problems. From both a pragmatic and empirical standpoint, we argue that the SM exclusionary clause is untenable, and that it deserves neither our support nor the continued professional focus that it continues to demand. Using the “Triangle of Support” model as an exemplar, we propose that assessment methods should be linked to comprehensive systems of service delivery to provide a true cascade of services for students with behavioral and emotional problems. Recommended alternative definitions of ED are discussed, including the National Coalition definition of Emotional and Behavioral Disorders that narrowly missed congressional approval for replacing the current definition. Further, we recommend adoption of the externalizing–internalizing broadband dimensional dichotomy as an emerging and scientifically sound alternative way of conceptualizing emotional and behavioral problems. © 2004 Wiley Periodicals, Inc. Psychol Schs 41: 899–910, 2004.
Shifting from categories to services: Comprehensive school‐based mental health for children with emotional disturbance and social maladjustment
Authors: Heathfield Lora Tuesday , Clark Elaine 
Published: October 2004

AbstractTo meet the present and future educational and mental health needs of our nation's youth, current models of mental health service delivery need to be reformed. Any more time spent arguing the differences between categories such as Emotional Disturbance (ED) and Social Maladjustment (SM) will only delay much needed services and deplete our already limited resources. Children's mental health needs are not being met in the current model of service delivery. It is proposed that school psychology facilitate the move toward a comprehensive school‐based mental health service model. This type of model is consistent with many of the 2002 Futures of School Psychology Conference goals. This model also recognizes the importance of children's social–emotional functioning in that positive mental health directly impacts the learning potential of children. Additionally, the comprehensive school‐based mental health service model emphasizes the importance of prevention and early intervention. These proactive strategies are desperately needed to more effectively meet the rising numbers of youth with mental health needs. By focusing on preventing emotional and behavioral disorders and intervening early at the onset of symptoms, students will no longer have to wait until they are classified as ED or SM to receive much needed services. School psychology can play a pivotal role in the reform efforts toward a comprehensive school‐based mental health service model that promotes positive mental health in all children. © 2004 Wiley Periodicals, Inc. Psychol Schs 41: 911–920, 2004.
Blocker efflux through blocked pores
Authors: Ronan Dawn , Sordé Nathalie , Matile Stefan 
Published: October 2004

AbstractThe objective of this paper is to clarify a frequent confusion that occurs with synthetic multifunctional pores: does molecular recognition by a synthetic pore exclude molecular translocation through the same pore? Evidence that this is not the case is provided with a set of competitive experiments using a rigid‐rod β‐barrel with internal histidine–arginine dyads as synthetic multifunctional pores (SMPs) as well as 8‐hydroxypyrene‐1,3,6‐trisulfonate (HPTS) as a fluorescent and 1,3,6,8‐pyrenetetrasulfonate (PTS) as a non‐fluorescent blocker. Direct evidence for the efflux of HPTS blockers through blocked SMPs is obtained by quenching of released HPTS with an externally added quencher. Blockage of blocker efflux through blocked pores was demonstrated by adding PTS as the opposing external blocker (KD = 3.3 μM). A Hill coefficient of n = 1.5 may indicate that binding of more than one PTS blocker is necessary to inhibit the efflux of HPTS blockers. Supported by structural information on blockage and selectivity from biological potassium channels, blocker efflux through blocked pores is discussed as being implicated in selectivity. Copyright © 2004 John Wiley & Sons, Ltd.
Correlation of relative rates of chromyl chloride oxidation and chromic acid oxidation of acyclic alkenes versus alkene IPs and HOMOs
Authors: Nelson Donna J. , Li Ruibo , Brammer Christopher 
Published: October 2004

AbstractPlots of logarithms of relative reaction rates of chromyl chloride oxidation and of chromic acid oxidation of alkenes (log krel values) versus alkene ionization potentials (IPs) and versus their highest occupied molecular orbital energy levels (HOMOs) demonstrate excellent correlations. Each plot has a similar appearance and shows a single line with a positive slope. The results indicate that the rate‐determining step of each title reaction involves an electrophilic attack on the alkene π‐bond without significant steric effects; this supports a proposed 2 + 3 cycloaddition mechanism and disfavors a proposed stepwise 2 + 2 cycloaddition mechanism. Comparison is made with other d0 transition metal complexes that oxidize alkenes. Copyright © 2004 John Wiley & Sons, Ltd.
Reactive micelles: nitroso group transfer from N‐methyl‐N‐nitroso‐p‐toluenesulfonamide to amphiphilic amines
Authors: García‐Río L. , Hervés P. , Leis J. R. , Mejuto J. C. , Rodríguez‐Dafonte P. 
Published: October 2004

AbstractThe reactivity of N‐methyl‐N‐nitroso‐p‐toluene sulfonamide (MNTS) towards n‐alkylamines in water and in micellar aggregates was studied. Kinetic constants in both media were obtained. The pseudophase micellar model allows a satisfactory prediction of the experimental behaviour in all cases. The value obtained for the micellar pseudophase rate constant, k, is lower than that in bulk water. The increase in the observed rate constant, ko, with n‐alkylamine concentration is due to an increase in the local concentration of reactants in the micellar surface. The differences between kw and k values is due to the polarity of micellar pseudophase being lower than that in bulk water. Copyright © 2004 John Wiley & Sons, Ltd.
Theoretical study of protonated xylenes: ethene elimination and H,C‐scrambling reactions
Authors: Arstad Bjørnar , Kolboe Stein , Swang Ole 
Published: October 2004

AbstractQuantum chemical calculations have been carried out to investigate various unimolecular rearrangements that can take place in protonated gas‐phase xylenes. Hydrogen and methyl group ring migrations were investigated. The barriers for hydrogen migrations are lower than the barriers for methyl group migrations. Mechanisms for ring expansion to seven‐membered rings, and for contraction to five‐membered rings were studied. Both of these mechanisms can eventually lead to ethene elimination. The most favourable ring expansion step goes through a 1,3‐hydrogen shift from a methyl group onto the arenium ring, forming a protonated methylcycloheptatriene. Interconversions between various ring‐expanded forms have been investigated. Re‐contraction can lead to an ethylbenzenium ion that could subsequently split off ethene. Alternatively, the xylenium ion can contract to a five‐membered ring. The immediate product is a bicyclic ion (bicyclo[3.1.0]hexane skeleton) that can rearrange further to give an ethylbenzenium ion, or the five‐ring system can split off ethene, and be converted into a cyclopentadienyl ion that can isomerize into a benzenium ion. Stable structures and transition states are calculated both at the B3LYP/cc‐pVTZ//B3LYP/6‐311G(d,p) and at the MP2/cc‐pVTZ//MP2/6‐31G(d) levels. The energies needed for ring expansion or ring contraction are not very different, and the calculations suggest that both reaction paths are possible, but the energy needed for actually splitting off an ethene molecule is lower along the expansion path. Copyright © 2004 John Wiley & Sons, Ltd.
A priori calculation of molecular properties to chemical accuracy
Authors: Helgaker Trygve , Ruden Torgeir A. , Jørgensen Poul , Olsen Jeppe , Klopper Wim 
Published: October 2004

AbstractQuantum chemical methods for the calculation of molecular properties to chemical accuracy are reviewed. We begin by reviewing wave‐function based electronic structure theory, with emphasis on coupled‐cluster theory and the description of electron correlation in terms of virtual excitations from occupied to virtual molecular orbitals. Next, we discuss the expansion of molecular orbitals in atomic orbitals and the design of one‐electron basis sets for correlated calculations at the coupled‐cluster level of theory. In particular, we discuss the convergence of the electronic energy in the principal expansion as realized in the correlation‐consistent basis sets. Following this theoretical introduction, we consider the accurate calculation of atomization energies, reaction enthalpies, dipole moments and spectroscopic constants such as bond distances and harmonic and anharmonic force constants. For each property, we identify what levels of theory in terms of basis set (the one‐electron description) and virtual excitation level (the N‐electron description) are needed for agreement with experiment to chemical accuracy, that is, about 1 kcal mol−1 (1 kcal = 4.184 kJ) for atomization energies and reaction enthalpies, about 0.1 pm for bond distances and about 1 cm−1 for vibrational frequencies. In each case, we consider in detail the direction and magnitude of the changes in the calculated properties with improvements in the one‐ and N‐electron descriptions of the electronic system, paying particular attention to the cancellation of errors arising from the simultaneous truncations of the coupled‐cluster expansion and the one‐electron basis set. We emphasize that agreement with experiment, even with chemical accuracy, for a few selected properties is by itself no guarantee of quality and should never be taken as indicative of an accurate description of the electronic system. To ensure such a description, the errors arising from the truncations of the one‐ and N‐electron expansions must be controlled by carrying out sequences of calculations, where the different levels of theory are systematically varied and where convergence is carefully monitored. Copyright © 2004 John Wiley & Sons, Ltd.
Catalytic dehydrogenation of ethane over mononuclear Cr(III) surface sites on silica. part I. C—H activation by σ‐bond metathesis
Authors: Lillehaug Sindre , Børve Knut J. , Sierka Marek , Sauer Joachim 
Published: October 2004

AbstractMononuclear Cr(III)–silica models have been studied by quantum chemical methods with respect to catalytic activity toward dehydrogenation of ethane. Both cluster and slab models have been developed and used to explore the conceptual model of mononuclear Cr(III) with three covalent ligands that coordinate through oxygen. The study focuses on a reaction mechanism consisting of three main reaction steps: (1) C—H activation of ethane according to σ‐bond metathesis and accompanied by the formation of O—H and Cr—C bonds, (2) β‐H transfer to chromium with subsequent loss of ethene and (3) regeneration of the chromium site under evolution of H2. An alternative mechanism is also explored, in which C—H activation takes place at a reactive hydridochromium complex. Stationary points pertaining to these reactions have been optimized, and free energy calculations are used to identify the rate‐determining steps. The influence of the local structure of the chromium surface sites is explored by means of a number of idealized surface models and electronic energy profiles for the reactions. Copyright © 2004 John Wiley & Sons, Ltd.
Additional evidence of possible structural effect of diol units in preformed oligoesters on solution copolycondensation with x,y‐dihydroxytoluenes and their isomers promoted by tosyl chloride/dimethylformamide/pyridine
Authors: Higashi Fukuji , Tsubonouchi Shingo 
Published: October 2004

AbstractA two‐stage copolycondensation of a mixture of equal parts of isophthalic acid and terephthalic acid was conducted using a tosyl chloride/dimethylformamide/pyridine condensing agent. In the initial stage x,y‐dihydroxytoluenes (x,y‐DHTs) or 2,4‐dihydroxyethylbenzene (2,4‐DHEB) was used and in the next stage isomeric DHTs or the DHEB was used. The results were examined in terms of how the reaction of the resulting oligomers with the next monomers proceeded, which was evaluated from distributions of the next monomers in the resultant copolymers as determined by 1H NMR. A structurally selective reaction was observed. The preformed oligomers from symmetrically substituted 3,5‐DHT reacted randomly with similarly substituted 2,6‐DHT or asymmetric 2,4‐DHEB, but those from 2,4‐DHEB reacted selectively with both of 3,5‐ and 2,6‐DHT. In the reactions of the oligomers from 2,6‐DHT, they reacted randomly with 2,6‐DHT but selectively with 2,4‐DHEB. Such selective reactions were also observed in the reaction of p‐isomeric 2,5‐DHT with the oligomers prepared from 3,5‐ or 2,6‐DHT. When the monomers were copolymerized simultaneously instead of stepwise, they distributed randomly in the resultant copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5687–5694, 2004
Intramolecular energy transferable (2,2‐diphenylvinyl)phenyl substituted poly(p‐phenylenevinylene) derivative with efficient photoluminescence and electroluminescence
Authors: Shin Dong‐Cheol , Kim Yun‐Hi , You Hong , Jin Jae Gyu , Kwon Soon‐Ki 
Published: October 2004

AbstractA poly(p‐phenylenevinylene) (PPV) derivative containing a bulky (2,2‐diphenylvinyl)phenyl group in the side chain, EHDVP‐PPV, was synthesized by Gilch route. The reduced tolane‐bisbenzyl (TBB) defects, as well as the structure of the polymer, was confirmed by various spectroscopic methods. The intramolecular energy transfer from the (2,2‐diphenylvinyl)phenyl side group to the PPV backbone was studied by UV‐vis and photoluminescence (PL) of the obtained polymer and model compound. The polymer film showed maximum absorption and emission peaks at 454 and 546 nm, respectively, and high PL efficiency of 57%. A yellow electroluminescence (λmax = 548 nm) was obtained with intensities of 6479 cd/m2 when the light‐emitting diodes of ITO/PEDOT/EHDVP‐PPV/LiF/Al were fabricated. The maximum power efficiency of the devices was 0.729 lm/W with a turn‐on voltage of 3.6 V. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5636–5646, 2004
Atom transfer radical polymerization of ionic liquid 2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate
Authors: Ding Shijie , Tang Huadong , Radosz Maciej , Shen Youqing 
Published: October 2004

AbstractPolymeric forms of ionic liquids may have many potential applications because of their high thermal stability and ionic nature. They are generally synthesized by conventional free‐radical polymerization. Here we report a living/controlled free‐radical polymerization of an ionic liquid monomer, 2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate (BIMT), via atom transfer radical polymerization. Copper bromide/bromide based initiator systems polymerized BIMT very quickly with little control because of fast activation but slow deactivation. With copper chloride as the catalyst and trichloroacetate, CCl4, or ethyl α‐chlorophenylacetate as the initiator, BIMT was polymerized at 60 °C in acetonitrile with first‐order kinetics with respect to the monomer concentration. The molecular weight was linearly dependent on the conversion. The monomer concentration strongly affected the polymerization: a low monomer concentration caused the polymerization to be incomplete, probably because of catalyst disproportionation in polar solvents. The addition of a small amount of pyridine suppressed such disproportionation, but a further increase in the amount of pyridine greatly slowed the polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5794–5801, 2004
Preparing a polystyrene‐functionalized multiple‐walled carbon nanotubes via covalently linking acyl chloride functionalities with living polystyryllithium
Authors: Huang Hsuan‐Ming , Liu I‐Chun , Chang Ching‐Yu , Tsai Hung‐Chieh , Hsu Chuan‐Hsiao , Tsiang Raymond Chien‐Chao 
Published: October 2004

AbstractA new method was developed for preparing polystyrene‐functionalized multiple‐walled carbon nanotubes (MWNTs) through the termination of anionically synthesized living polystyryllithium with the acyl chloride functionalities on the MWNTs. The acyl chloride functionalities on the MWNTs were in turn obtained by the formation of carboxyls via chemical oxidation and their conversion into acyl chlorides. The polystyrene‐functionalized MWNTs had good dispersion in common organic solvents, and this indicated good compatibility for the preparation of styrenic nanocomposite materials. The synthesis results and characterization data for the functionalized MWNTs, collected via Fourier transform infrared, thermogravimetric analysis, solid‐state NMR, and electron microscopy, are presented and discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5802–5810, 2004
MSDsite: A database search and retrieval system for the analysis and viewing of bound ligands and active sites
Authors: Golovin Adel , Dimitropoulos Dimitris , Oldfield Tom , Rachedi Abdelkrim , Henrick Kim 
Published: October 2004

AbstractThe three‐dimensional environments of ligand binding sites have been derived from the parsing and loading of the PDB entries into a relational database. For each bound molecule the biological assembly of the quaternary structure has been used to determine all contact residues and a fast interactive search and retrieval system has been developed. Prosite pattern and short sequence search options are available together with a novel graphical query generator for inter‐residue contacts. The database and its query interface are accessible from the Internet through a web server located at: http://www.ebi.ac.uk/msd‐srv/msdsite. Proteins 2005. © 2004 Wiley‐Liss, Inc.
All‐atom folding of the three‐helix HIV accessory protein with an adaptive parallel tempering method
Authors: Schug A. , Herges T. , Wenzel W. 
Published: October 2004

AbstractAll‐atom protein structure prediction from the amino acid sequence alone remains an important goal of biophysical chemistry. Recent progress in force field development and validation suggests that the PFF01 free‐energy force field correctly predicts the native conformation of various helical proteins as the global optimum of its free‐energy surface. Reproducible protein structure prediction requires the availability of efficient optimization methods to locate the global minima of such complex potentials. Here we investigate an adapted version of the parallel tempering method as an efficient parallel stochastic optimization method for protein structure prediction. Using this approach we report the reproducible all‐atom folding of the three‐helix 40 amino acid HIV accessory protein from random conformations to within 2.4 Å backbone RMS deviation from the experimental structure with modest computational resources. Proteins 2004. © 2004 Wiley‐Liss, Inc.
Effects of mutations in tyrosine hydroxylase associated with progressive dystonia on the activity and stability of the protein
Authors: Royo Montserrat , Daubner S. Colette , Fitzpatrick Paul F. 
Published: October 2004

AbstractTyrosine hydroxylase (TyrH) catalyzes the conversion of tyrosine to dihydroxyphenylalanine (DOPA), the rate‐limiting step in the biosynthesis of dopamine. Four mutations in the TyrH gene have recently been described in cases of autosomal recessive DOPA‐responsive dystonia (Swaans et al., Ann Hum Genet 2000;64:25–31). All four are predicted to result in changes in single amino acid residues in the catalytic domain of the protein: T245P, T283M, R306H, and T463M. To determine the effects of these mutations on the molecular properties of the enzyme, mutant proteins containing the individual single amino acid changes have been expressed in bacteria and purified. Only the T283M mutation results in a decrease in the enzyme kcat value, while the T245P enzyme has a slightly higher value than the wild‐type enzyme. The only case in which a Km value for either tyrosine or tetrahydrobiopterin is perturbed is the T245P enzyme, for which the Km value for tyrosine has increased about 50%. In contrast to the minor effects of the mutations on enzyme activity, the stability is decreased significantly by the mutations. The R306H and T283M enzymes are the least stable, losing activity 30‐ and 50‐fold more rapidly than the wild‐type enzyme. The apparent Tm value for unfolding was decreased by 3.9, 8.2, and 7.2° for the T245P, R306H, and T463M enzymes, while the T283M enzyme was too unstable for measurement of a Tm value. The results establish that the physiological effects of the mutations are primarily due to the decreased stability of the mutant proteins rather than decreases in their intrinsic activities. Proteins 2005. © 2004 Wiley‐Liss, Inc.
The anti‐platelet approach targeting the fibrinogen ligand of the GPIIb/IIIa receptor
Authors: Tsikaris Vassilios 
Published: October 2004

AbstractActivation of the platelet surface receptor GPIIb/IIIa is the final pathway of platelet aggregation, regardless of the initiating stimulus. RGD analogues, peptidomimetics and monoclonal antibodies to GPIIb/IIIa have been developed targeting the blockage of the receptor and inhibition of the fibrinogen binding. However, the intrinsic activating effect of GPIIb/IIIa blockers is widely discussed as one potential contributing factor for the disappointing outcome of trials with GPIIb/IIIa inhibitors. An alternative method for thrombus prevention could be the use of specific fibrinogen blockers since they will act at the final step of the platelet aggregation and are expected to leave the receptor unaffected. To achieve this target the design of the fibrinogen ligands could be based on (i) sequences derived from GPIIb/IIIa ligand binding sites, and (ii) sequences complementary to RGD and/or to fibrinogen γ‐chain. The available information, which could be used as a starting point for developing potent fibrinogen ligands, is reviewed. Copyright © 2004 European Peptide Society and John Wiley & Sons, Ltd.
BAM‐L002—a new type of certified reference material for length calibration and testing of lateral resolution in the nanometre range
Authors: Senoner M. , Wirth Th. , Unger W. , Österle W. , Kaiander I. , Sellin R. L. , Bimberg D. 
Published: October 2004

AbstractA new type of test sample for the determination of lateral resolution in surface analysis is presented. The certified reference material BAM‐L002 ‘Nanoscale strip pattern for length calibration and testing of lateral resolution’ is an embedded cross‐section of epitaxially grown layers of AlxGa1−xAs and InxGa1−xAs on GaAs substrate. The surface of the sample provides a flat pattern with strip widths of 0.4–500 nm. The combination of gratings, isolated narrow strips and sharp edges of wide strips offers improved possibilities for the calibration of a length scale, the determination of lateral resolution and the optimization of instrument settings. The feasibility of the reference material for an analysis of lateral resolution is demonstrated for SIMS. Copyright © 2004 John Wiley & Sons, Ltd.