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  • 1995-1999  (2,116)
  • 1965-1969  (1,973)
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  • Psychopharmacology
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Der Nervenarzt 70 (1999), S. 1-10 
    ISSN: 1433-0407
    Keywords: Schlüsselwörter Tic-Störung ; Zwangsstörung ; Kinder ; Jugendliche ; Neurobiologie ; Psycho- pharmakologie ; Verhaltenstherapie ; Key words Tic-disorder ; Obsessive-compulsive disorder ; Children ; Adolescents ; Neurobiology ; Psychopharmacology ; Behavior therapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary In children and adolescents motor/vocal tics and obsessive-compulsive behavior are known to be closely related. Thereby, a continuum of symptoms ranging from single tics to a mixed picture of tics/rituals/obsessive-compulsive traits to clinically relevant obsessions and compulsions could be described. As neurobiological substrates dysfunctions in corresponding cortico-striato-thalamo-cortical circuits (sensorimotor circuit in tic symptomatology, orbitofrontal circuit in obsessive-compulsive behavior) were postulated. For both disturbances behavioral therapy can be used to improve control mechanisms to counterregulate tics and obsessive-compulsive behavior, respectively, and psychopharmacological agents can be administerd to compensate dysbalances in neurotransmitter systems. In case of a mixed symptomatologic picture it is necessary to include interventions for both pols of the symptom-continuum in the therapeutic programme to achieve extensive improvement as a basis for a further positive development of the patient.
    Notes: Zusammenfassung Motorische/vokale Tics und zwanghafte Verhaltensweisen kommen bei Kindern und Jugendlichen häufig gemeinsam vor; dabei kann ein Symptomkontinuum von solitär auftretenden Tics über ein Mischbild von Tics und Ritualen/zwanghaften Gedanken und/oder Handlungen bis hin zu eindeutigen Zwangsphänomenen beschrieben werden. Neurobiologisch können diesem Symptomkontinuum unterschiedlich ausgebreitete Dysfunktionen entsprechender kortiko-striato-pallido-thalamo-kortikaler Regulationssysteme zugrunde liegen. Therapeutisch lassen sich bei beiden Verhaltensauffälligkeiten mittels verhaltenstherapeutischer Techniken Steuerungs- und Kontrollmöglichkeiten zur Gegenregulation der Auffälligkeiten verbessern sowie durch Einsatz von Psychopharmaka Dysbalancen von Neurotransmittersystemen ausgleichen. Bei einem Mischbild von Tics und Zwängen sind therapeutische Interventionen für beide Zielbereiche erforderlich. Nur so können umfassende Verbesserungen erreicht und günstige Entwicklungsbedingungen für die betroffenen Kinder und Jugendlichen eröffnet werden.
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  • 2
    ISSN: 1437-7799
    Keywords: Key words Peritoneal dialysis ; Peritonitis ; Cat ; Pasteurella multocida
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A 49-year-old man had three episodes of bacterial peritonitis in the 8 months after he started nocturnal intermittent peritoneal dialysis (NIPD) at home, using an automated cycler device. When peritonitis was first diagnosed, Enterobacter agglomerance was cultured in his peritoneal fluid. In the second and third episodes, Pasteurella multocida and alpha-Streptococcus were isolated, respectively. These bacteria are unusual pathogens in continuous ambulatory peritoneal dialysis (CAPD) peritonitis. Detailed questioning revealed that a domestic cat had bitten the dialysis tube before the patient experienced the second episode of peritonitis. Pasteurella multocida is part of the normal oral flora in cats and dogs. We isolated Pasteurella multocida from the teeth of the patient's cat. Enterobacter agglomerance is part of the common bacterial flora in animal's alimentary tract, and alpha-Streptococcus is commonly found in animal's respiratory tracts. Since the patient removed the cat from his bedroom, he has had no peritonitis. NIPD is a very convenient sysytem for patients in the final stage of renal failure; however, patients must be aware of the risks associated with keeping pets in their homes. This case is the first report of cat-associated peritonitis in Japan.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 128 (1999), S. 527-530 
    ISSN: 1432-1106
    Keywords: Key words Nucleus reticularis gigantocellularis ; Reticulospinal neuron ; Neck motoneuron ; Single-neuron EPSP ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Functional connections of single reticulospinal neurons (RSNs) in the nucleus reticularis gigantocellularis (NRG) with ipsilateral dorsal neck motoneurons were examined with the spike-triggered averaging technique. Extracellular spikes of single NRG-RSNs activated antidromically from the C6, but not from the L1 segment (C-RSNs) were used as the trigger. These neurons were monosynaptically activated from the superior colliculus and the cerebral peduncle. Single-RSN PSPs were recorded in 43 dorsal neck motoneurons [biventer cervicis and complexus (BCC) and splenius (SPL)] for 21 NRG-RSNs and 135 motoneurons tested. All synaptic potentials were EPSPs, and most of their latencies, measured from the triggering spikes, were 0.8–1.5 ms, which is in a monosynaptic range. The amplitudes of single-RSN EPSPs were 10–360 µV. Spike-triggered averaging revealed single-RSN EPSPs in multiple motoneurons of the same species (SPL or BCC), their locations extending up to nearly 1 mm rostrocaudally. Synaptic connections of single RSNs with both SPL and BCC motoneurons were also found with some predominance for one of them. The results provide direct evidence that NRG-RSNs make monosynaptic excitatory connections with SPL and BCC motoneurons. It appears that some NRG-RSNs connect predominantly with SPL motoneurons and others with BCC motoneurons.
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  • 4
    ISSN: 1432-1106
    Keywords: Key words Abdominal muscles ; Back muscles ; Motoneurons ; Cutaneous afferent ; Spinal cord ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Postsynaptic potentials (PSPs) evoked in motoneurons innervating the back and abdominal muscles in the lumbar part of the body by stimulating hindlimb cutaneous afferents were investigated in unanesthetized decerebate and spinal cats. Various types of PSP: pure excitatory postsynaptic potential (EPSP), pure inhibitory postsynaptic potential (IPSP), and mixed PSP (i.e., EPSP followed by IPSP, EPSP/IPSP; and IPSP followed by EPSP, IPSP/EPSP) were observed. The weak stimulation at 2 times threshold (2T) produced predominantly the EPSP, while at 5T the incidence of IPSP or EPSP followed by IPSP was increased. In about 20–50% of the various groups of motoneurons, PSPs evoked by ipsi- and contralateral nerves were qualitatively and quantitatively similar. For the other motoneurons, PSPs evoked by ipsi- and contralateral nerves were markedly different with respect to magnitude and/or polarity. These findings suggest that, within each motoneuron pool, some neurons act to increase stiffness of the trunk or to move vertically in response to an increased activity of cutaneous afferents, while the other motoneurons act to produce lateral bending of the trunk.
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  • 5
    ISSN: 1432-1106
    Keywords: Key words Retinal ganglion cells ; Axonal regeneration ; Single-unit activity ; Receptive field ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Receptive-field properties of retinal ganglion cells (RGCs) that had regenerated their axons were studied by recording single-unit activity from strands teased from peripheral nerve (PN) grafts apposed to the cut optic nerve in adult cats. Of the 286 visually responsive units recorded from PN grafts in 20 cats, 49.7% were classified, according to their receptive-field properties, as Y-cells, 39.5% as X-cells, 6.6% as W-cells, and 4.2% were unclassified. The predominant representation of Y-cells is consistent with a corresponding morphological study (Watanabe et al. 1993a), which identified α-cells as the RGC type with the largest proportion of regenerating axons. Among the X-cells, we only found ON-center types, whereas both ON-center and OFF-center Y-cells were found. As in intact retinas, the receptive-field center sizes of Y-cells and W-cells were larger than those of X-cells at corresponding displacements from the area centralis. Within the 10° surrounding the area centralis, the receptive fields of X-cells with regenerated axons were larger than those in intact retinas, suggesting that some rearrangement of retinal circuitry occurred as a consequence of degeneration and regeneration. Receptive-field center responses of Y-, X-, and W-type units with regenerated axons were similar to those found in intact retinas, but the level of spontaneous activity of Y- and X-type units was, in general, less than that of intact RGCs. Receptive-field surrounds were weak or not detected in more than half of the visually responsive RGCs with regenerated axons.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 125 (1999), S. 184-199 
    ISSN: 1432-1106
    Keywords: Key words Corticospinal tract ; Motor cortex ; Activity-dependent development ; Spinal cord ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Corticospinal (CS) axon terminations in several species are widespread early in development but are subsequently refined into a spatially more restricted distribution. We studied the role of neural activity in sensorimotor cortex in shaping postnatal development of CS terminations in cats. We continuously infused muscimol unilaterally into sensorimotor cortex to silence neurons during the postnatal CS refinement period (weeks 3–7). Using anterograde transport of WGA-HRP, we examined the laterality of terminations from the muscimol-infused (i.e., silenced) and active sides in the spinal cord, as well as in the cuneate nucleus and red nucleus. We found that CS terminations from the muscimol-infused cortex were very sparse and limited to the contralateral side, while those from the active cortex maintained an immature bilateral topography. Controls (saline infusion, noninfusion) had dense, predominantly contralateral, CS terminations. There was a substantial decrease in the spinal gray matter area occupied by terminations from the side receiving the blockade and a concomitant increase in the area occupied by ipsilateral terminations from the active cortex. Optical density measurements of HRP reaction product from the active cortex in muscimol-infused animals showed substantial increases over controls in the ratio of ipsilateral to contralateral CS terminations for all laminae examined (IV–V, VI, VII). Our findings suggest that ipsilateral dorsal horn terminations reflect new axon growth during the refinement period because they are not present there earlier in development. Those in the ventral horn are present earlier in development and thus could reflect maintenance of transient terminations. Increased ipsilateral terminations from active cortex were due to recrossing of CS axons in lamina X and not to an increase in labeled CS axons in the ipsilateral white matter. Examination of brain stem terminations suggested that, between postnatal weeks 3 and 7, development of corticocuneate terminations also is activity-dependent but that development of corticorubral terminations is not. Activity-dependent CS development is a plausible mechanism by which early motor experiences could shape the anatomical and functional organization of the motor systems during a critical postnatal period.
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  • 7
    ISSN: 1432-1106
    Keywords: Key words Omnipause neurons ; OPN ; Saccade ; Gaze shift ; Tracking ; Perisaccadic drifts ; Moving target ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Pontine omnipause neurons (OPNs) have so far been considered as forming a homogeneous group of neurons whose tonic firing stops during the duration of saccades, when the head is immobilized. In cats, they pause for the total duration of gaze shifts, when the head is free to move. In the present study, carried out on alert cats with fixed heads, we present observations made during self-initiated saccades and during tracking of a moving target which show that the OPN population is not homogeneous. Of the 76 OPNs we identified, 39 were found to have characteristics similar to those of previously described neurons, ”saccade” (S-) OPNs: (1) the durations of their pauses were significantly correlated with the durations of saccades; (2) the discharge ceased shortly before saccade onset and resumed before saccade end; (3) visual responses to target motion were excitatory; and (4) during tracking, S-OPNs interrupted the discharge for the duration of saccades and resumed firing during perisaccadic ”drifts”. However, the characteristics of 37 neurons (”complex” (C-) OPNs) were different: (1) the pause duration was not correlated with the duration of self-initiated saccades; (2) time lead of pause onsets relative to saccades was, on average, longer than in the group of S-OPNs, and firing resumed after the saccade end; (3) visual target motion suppressed tonic discharges; and (4) during tracking, firing was interrupted for the total duration of gaze shifts, including not only saccades but also perisaccadic ”drifts”. We conclude that cat OPNs can be subdivided into two main groups. The first comprises neurons whose firing patterns are compatible with gating individual saccades (”saccade” OPNs). The second group consists of ”complex” OPNs whose firing characteristics are appropriate to gate total gaze displacements rather than individual saccades. The function of these neurons may be to disinhibit pontobulbar circuits participating in the generation of saccade sequences and associated perisaccadic drifts.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 126 (1999), S. 410-416 
    ISSN: 1432-1106
    Keywords: Key words Vestibulocollic reflex ; Saccular nerve ; Utricular nerve ; Sternocleidomastoid motoneuron ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Connections from the otolithic organs to sternocleidomastoid (SCM) motoneurons were studied in 20 decerebrate cats. The electrical stimulation was selective for the saccular or the utricular nerves. Postsynaptic potentials were recorded from antidromically identified SCM motoneurons; these muscles participate mainly in neck rotation and flexion. Partial transections of the brainstem at the level of the obex were performed to identify the possible pathway from the otolithic organs to the SCM motoneurons. Saccular or utricular nerve stimulation mainly evoked inhibitory postsynaptic potentials (IPSPs) in the ipsilateral SCM motoneurons. Some of the sacculus-induced IPSPs were preceded by small-amplitude excitatory PSPs (EPSPs). The latencies of the PSPs ranged from 1.8 to 3.1 ms after saccular nerve stimulation and from 1.7 to 2.8 ms after utricular nerve stimulation, indicating that most of the ipsilateral connections were disynaptic. In the contralateral SCM motoneurons, saccular nerve stimulation had no or faint effects, whereas utricular nerve stimulation evoked EPSPs in about two-thirds of neurons, and no visible PSPs in about one-third of neurons. The latencies of the EPSPs ranged from 1.5 to 2.0 ms, indicating the disynaptic connection. Thus, the results suggest a difference between the two otolithic innervating patterns of SCM motoneurons. After transection of the medial vestibulospinal tract (MVST), saccular nerve stimulation did not evoke IPSPs at all in ipsilateral SCM motoneurons, but some (11/40) neurons showed small-amplitude EPSPs. Most (24/33) of the utricular-activated IPSPs disappeared after transection, whereas the other 9 neurons still indicated IPSPs. In the contralateral SCM motoneurons, no utricular-activated EPSPs were recorded after transection. These MVST transection results suggest that most of the otolith-SCM pathways are located in the MVST at the obex level. However, the results also suggest the possibility that other otolith-SCM pathways exist at the obex level.
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  • 9
    ISSN: 1432-1106
    Keywords: Key words Vestibulo-ocular reflex ; Vertigo ; Labyrinthectomy ; Compensation ; Motor learning ; Oculomotor ; Plasticity ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Accurate performance by the vestibulo-ocular reflex (VOR) is necessary to stabilize visual fixation during head movements. VOR performance is severely affected by peripheral vestibular damage; after one horizontal semicircular canal is plugged, the horizontal VOR is asymmetric and its amplitude is reduced. The VOR recovers partially. We investigated the limits of recovery by measuring the VOR’s response to ipsilesional and contralesional rotation after unilateral peripheral damage in cats. We found that the VOR’s response to rotation at high frequencies remained asymmetric after recovery was complete. When the stimulus was a pulse of head velocity comprising a dynamic overshoot followed by a plateau, gain was partially restored and symmetry completely restored within 30 days after the plug, but only for the plateau response. The overshoot in eye velocity remained asymmetric. The asymmetry was independent of stimulus velocity throughout the known linear velocity range of primary vestibular afferents. Sinusoidal rotation at 0.05–8 Hz revealed that, within this range, the persistent asymmetry was significant only at frequencies above 2 Hz. Asymmetry was independent of the peak head acceleration over the range of 50–500°/s2. When both horizontal canals were plugged, a small residual VOR was observed, suggesting residual signal transduction by plugged semicircular canals. However, transduction by plugged canals could not explain the enhancement of the VOR gain, at high frequencies, for rotation away from the plugged side compared with rotation toward the plug. Also, the high-frequency asymmetry was present after recovery from a unilateral labyrinthectomy. These results suggest that high-frequency asymmetry after unilateral damage is not due to residual function in the plugged canal. The findings are discussed in the context of a bilateral model of the VOR that includes central filtering.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 129 (1999), S. 483-493 
    ISSN: 1432-1106
    Keywords: Key words Vestibulocollic reflex ; Short-latency pathways ; Vestibulospinal and reticulospinal pathways ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The purpose of this review is to assess the role of short-latency pathways in the vestibulocollic reflex (VCR). First the current knowledge about the disynaptic and trisynaptic pathways linking semicircular canal and otolith afferents with cat neck motoneurons is summarized. We then discuss whether these pathways are sufficient or necessary to produce the responses observed in neck muscles by natural vestibular stimulation and conclude that they are neither. Finally, alternate pathways are considered, most likely involving reticulospinal fibers, which are an important part of the neural substrate of the VCR.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 146 (1999), S. 339-347 
    ISSN: 1432-2072
    Keywords: Key words Hyperbolic discounting ; Impulsivity ; Self-control ; Reward bundling ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Animal studies of impulsivity have typically used one of three models: a delay of reward procedure, a differential reinforcement for low rate responding (DRL) procedure, or an autoshaping procedure. In each of these paradigms, we argue, measurement of impulsivity is implicitly or explicitly equated with the effect delay has on the value of reward. The steepness by which delay diminishes value (the temporal discount function) is treated as an index of impulsivity. In order to provide a better analog of human impulsivity, this model needs to be expanded to include the converse of impulsivity – self-control. Through mechanisms such as committing to long range interests before the onset of temptation, or through bundling individual choices into classes of choices that are made at once, human decision-making can often look far less myopic than single trial experiments predict. For people, impulsive behavior may be more often the result of the breakdown of self-control mechanisms than of steep discount functions. Existing animal models of self-control are discussed, and future directions are suggested for psychopharmacological research.
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  • 12
    ISSN: 1432-0568
    Keywords: Key words Claustrum ; Visual cortex ; Visual zones Comparative anatomy ; Rat ; Guinea pig ; Rabbit ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The retrograde axonal transport method was used to compare the topography and organization of the visual zone of the claustrum in rat, guinea pig, rabbit and cat. First, massive Fluoro-Gold injections were placed into the primary visual cortex and the secondary areas. Experiments showed differences in the location of the visual zone among the animals under study. In rat, the visual zone occupied the posteroventral part of the claustrum and spread to its anterior pole. In guinea pig, neurons projecting to the visual cortex were located dorsally in the posterior half of the claustrum. In rabbit, similarly to the rat, they were localized in the posteroventral part; however, they did not reach the anterior pole. In cat, neurons that project to the visual cortex were concentrated dorsally in the posterior fourth of the claustrum. In double-injection experiments, Fast Blue and Diamidino Yellow were placed into the primary and secondary visual areas in various combinations. The experiments showed that in the rat and the rabbit claustral neurons project to primary visual cortex (area 17) as well as to both secondary visual areas (areas 18a and b). Populations of neurons sending axons to the primary and secondary areas showed full overlap. The presence of double-labeled neurons indicates that some claustral neurons project both to the primary and secondary fields. In cat, neurons that project to the primary visual cortex appear to be clearly separated from those connected with the secondary visual area, as no double-labeled neurons were found. In all studied species, the double injections placed into the visual and primary somatosensory cortex did not result in any double-labeling neurons. Our results indicate that the location of the visual zone in the posterior part of the claustrum is a phylogenetically stable feature, whereas its dorsoventral shift as well as the extent toward the anterior pole is related to the particular species. The overlap of neurons projecting to the primary and secondary visual areas in the rat and rabbit as well as the separation of both projections in cat appear to reflect the higher degree of complexity of the visual system in the latter.
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  • 13
    ISSN: 1432-1106
    Keywords: Key words Positron emission tomography ; Articular nociception ; Cerebral blood flow ; Joint inflammation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  In cats the global (gCBF) as well as the regional cerebral blood flow (rCBF) and blood pressure were measured before, during, and after noxious inward and outward rotations of normal and inflamed elbow joints. The animals were anesthetized with halothane and immobilized by gallamine triethiodide. The gCBF as well as the rCBF were measured using positron emission tomography (PET) with a camera specifically designed for use in small animals. Slow intravenous bolus injections of 15O-labeled water were followed by 3-min acquisition of regional radioactivity starting at the time of injection. In all experiments the gCBF as well as the blood pressure were increased by noxious inward-outward rotations of the normal and of the inflamed joint, whereas the blood pressure and the rCBF remained unchanged during bolus injections under control conditions (without any joint movement). Movements of the inflamed joint evoked significantly greater increases in blood pressure and gCBF than corresponding ones of the normal joint. These increases in gCBF were paralleled by increases in rCBF along the complete anterior to posterior axis of the brain. Again, the increases in rCBF were larger, more extensive and more uniform following the stimulation of the inflamed joint relative to the results obtained with stimulation of the normal joint. No significant laterality was seen, but when an atlas-based region of interest (ROI) analysis was carried out and when the individual variations in rCBF were removed with two-way ANOVA, significant differences were disclosed in rCBF between the stimulated condition and the resting condition in a large number of brain regions. In particular, noxious rotation of the normal (right) elbow joint induced a significant increase in rCBF over the cerebral cortex and in the right thalamus and hippocampus. The same stimulation of the (left) inflamed joint induced a significant increase in rCBF throughout the brain; the biggest increase being over the right posterior cortex. It is concluded that under the conditions of the present experiments the generally accepted autoregulation of the cerebral blood flow is not fully functioning, and various factors that may be responsible for this failure (which obscures rCBF differences) are discussed. The more pronounced increases in rCBF when moving inflamed joints instead of normal ones is thought to be a direct consequence of the peripheral sensitization of the articular nociceptors and the consequent central hyperexcitability induced in the articular nociceptive pathways.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 122 (1998), S. 175-184 
    ISSN: 1432-1106
    Keywords: Key words Balance ; Sensorimotor transformation ; Neck proprioception ; Vestibular system ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  This study examined (1) how changes in head position affect postural orientation variables during stance and (2) whether changes in head position affect the rapid postural response to linear translation of the support surface in the horizontal plane. Cats were trained to stand quietly on a moveable platform and to maintain five different head positions: center, left, right, up, and down. For each head position, stance was perturbed by translating the support surface linearly in 16 different directions in the horizontal plane. Postural equilibrium responses were quantified in terms of the ground reaction forces, kinematics, dynamics (net joint torques), body center of mass, and electromyographic (EMG) responses of selected limb and trunk muscles. A change in head position involved rotation of not only the neck but also the scapulae and anterior trunk. Tonic EMG levels were modulated in several forelimb and scapular muscles but not hindlimb muscles. Finally, large changes in head orientation in both horizontal and vertical planes did not hamper the ability of cats to maintain postural equilibrium during linear translation of the support surface. The trajectory of the body’s center of mass was the same, regardless of head position. The main change was observed in joint torques at the forelimbs evoked by the perturbation. Evoked EMG responses of forelimb and scapular muscles were modulated in terms of magnitude but not spatial tuning. Hindlimb responses were unchanged. Thus, the spatial and temporal pattern of the automatic postural response was unchanged and only amplitudes of evoked activity were modulated by head position.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 122 (1998), S. 203-213 
    ISSN: 1432-1106
    Keywords: Key words Saccadic suppression ; Corollary discharge ; Visually evoked potential ; Striate cortex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Visually evoked potentials (VEPs) measured under conditions of retinal image stabilization that minimized the influences of visual masking and smearing were averaged from electroencephalographic records measured from striate cortex of three cats. The amplitudes of the VEPs increased around saccade initiation. The grating-evoked potentials obtained at different times relative to the saccade exhibited changes in waveform shape that could be attributed to a saccade-evoked potential. The changes in the shape of the waveform were reasonably accounted for by the summation of the grating-evoked potential (produced when the cat did not make a saccade) and an appropriately timed saccade-evoked potential. The fundamental amplitudes of the residual potentials were computed and found to vary across the time course of the saccade. These observations suggest that there are other influences besides visual masking that are exerted early in the visual pathway to modulate visual processing during saccadic eye movements. A corollary discharge process is the most likely candidate to exert these influences.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 122 (1998), S. 214-226 
    ISSN: 1432-1106
    Keywords: Key words Visual perception ; Three-dimensional motion ; Motion disparity ; Size change ; Posteromedial lateral suprasylvian cortex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The neuronal responsiveness to three-dimensional (3D) motion in cat posteromedial lateral suprasylvian (PMLS) cortex was studied using a computer-controlled, stereoscopic 3D graphic display capable of reproducing the major visual cues for natural 3D motion, including motion disparity, size, texture, and shading changes. The animals were anesthetized with nitrous oxide supplemented with alphaxalone, and paralysis prevented eye movement. Systematic investigation of neuronal responsiveness to 3D motions in 26 different directions revealed that more than half of the PMLS cells were selectively responsive to approaching (AP cells, 112 of 271) or recessive motion (RC cells, 64 of 271). The remaining cells were selectively responsive to frontoparallel motion (FP cells, 49 of 271) or nonselectively responsive to motion in multiple directions (NS cells, 46 of 271). The dependency on these visual cues was investigated as a reduction in the response amplitude or the response selectivity for the removal of a single cue from the motion stimuli containing the full visual cues. The AP and RC cells showed a strong dependency on the motion disparity cue, moderate dependency on the size cue, and weak dependency on the texture and shading cues. The FP cells showed no dependency on those visual cues. The cue dependency analysis indicated the existence of nonlinear interactions between those visual cues. Comparison of the responses to a combination of the motion disparity and size cues with the summed responses to each of the individual cues revealed that the responses to the combined cues are roughly predicted as a linear sum between the preferred responses. This comparison also showed nonlinear summation between the nonpreferred responses, i.e., responses to the combined cues were smaller than the summed responses. A similar quasilinear summation of the preferred responses between the two eyes and a nonlinear summation of the nonpreferred responses were found in the AP and RC cells for the motion disparity stimulus. All of these observations indicate that quasilinear and nonlinear interactions of the responses to various stimulus elements underlie the 3D motion responsiveness of the PMLS cells.
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  • 17
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    Springer
    Experimental brain research 119 (1998), S. 391-398 
    ISSN: 1432-1106
    Keywords: Key words Mechanoreceptor ; Axoplasm ; Muscle spindle ; Colchicine ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The experiments reported here demonstrate that the mechanical sensitivity of peripheral nerve fibres typically seen after injury can be induced without overtly injuring the nerve, but by simply applying colchicine topically to the nerve. In cats anaesthetised with pentobarbitone sodium, the medial gastrocnemius nerve was exposed and 10 mM colchicine applied topically for 15 min. The animals recovered from the operation normally and showed no subsequent motor deficit. Six days later animals were re-anaesthetised, a laminectomy carried out and responses recorded in single afferents at the level of the dorsal root. It was found that many afferents, particularly those with conduction velocities in the group II–III range, had become sensitive to local mechanical stimulation of the nerve in the region treated with colchicine and showed slowly adapting responses to stretch of the nerve. Many of the smaller fibres exhibited spontaneous activity. Mechanically sensitive afferents exhibited impulse conduction blocks at the colchicine-treated site. Some afferents, which appeared to conduct impulses normally through the treated region, were associated with muscle receptors having normal response properties. However, other muscle receptors were clearly abnormal and were insensitive to muscle stretch or contraction or exhibited only phasic responses. When the nerve was cut proximal to the colchicine-treated site, some, but not all, spontaneous activity was abolished. It was subsequently shown using a collision technique that the activity in some axons had its origin in the cell body in the dorsal root ganglion. In one experiment, it was shown that after nerve section proximal to the colchicine-treated region three of five axons switched their activity from a peripheral to a central origin. It is postulated that colchicine disrupts fast axonal transport of mechanically sensitive or voltage-sensitive ion channels, from the cell body to the peripheral terminals of the axons, leading to an accumulation of these channels at the treated site. This induces mechanical sensitivity and spontaneous activity. It is postulated that interruption of a retrogradely transported signal induces the spontaneous activity in the cell body. These experiments suggest that an important influence is exerted by the cell body on the peripheral terminals of mechanoreceptors to confer on them their normal response properties.
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  • 18
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    Experimental brain research 118 (1998), S. 1-13 
    ISSN: 1432-1106
    Keywords: Key words Nerve injury ; Retrograde reaction ; Spinal cord ; Electron microscopy ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The aim of this electron-microscopic study was to analyze the distribution of synaptic contacts on the cell bodies and dendrites of permanently axotomized adult cat spinal α-motoneurons. Following transection and ligation of the medial gastrocnemius nerve, the synaptic covering of the cell bodies and three different dendritic compartments of homonymous α-motoneurons was analyzed quantitatively at 3, 6, and 12 weeks postoperatively. The synaptic boutons were classified according to their size and the shape of their synaptic vesicles. On the soma, a transient increase in the number of boutons was noted at 3 weeks and 6 weeks postoperatively, while after 12 weeks the bouton number had decreased to half of its normal value. The transient increase was mainly due to an increase in the number of F-type boutons. At 12 weeks postoperatively, the synaptic covering was reduced by 83% on the soma and by 57% on the proximal dendrites. In the distal dendritic regions, the values for synaptic covering remained largely unchanged. In summary, axotomized motoneurons exhibit a reduction in synaptic covering which is maximal on the cell body and becomes less pronounced centrifugally along the dendrites. However, if also taking into account the loss of distal dendritic branches that occurs in axotomized motoneurons, the total loss of boutons is several times larger in the dendrites than on the soma.
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  • 19
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    Experimental brain research 118 (1998), S. 14-18 
    ISSN: 1432-1106
    Keywords: Key words Subcutaneous formalin ; Dorsal horn ; Nociception ; Central neuronal changes ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  In our previous report we found that subcutaneous (s.c.) formalin injection into the cutaneous receptive field (RF) of dorsal horn wide-dynamic-range (WDR) units and nociceptive primary afferent units resulted in a tonic, long-lasting increase in firing. However, s.c. formalin injection only resulted in a short-lasting increase in firing of non-nociceptive primary afferent units. In the present study, by using extracellular single-unit recording techniques we further studied effects of s.c. formalin on response properties of identified superficial-layer nociceptive-specific (NS) units and deeper-layer, low-threshold mechanoreceptive (LTM) units of L7 dorsal horn in urethane-chloralose-anesthetized cats. s.c. formalin injection into the RF of NS units resulted in a tonic, long-lasting increase in firing (7.08 ± 0.42 spikes/s, n = 5), for more than 1 h, compared with the spontaneous background (1.42 ± 0.03 spikes/s, n = 5). Formalin injection into the RF of LTM units also resulted in an increase in firing; however, the duration was short-lasting, for 25–520 s (152.92 ± 46.73 s, n = 12). The present study demonstrated that s.c. injection of dilute formalin solution resulted in activation of not only nociceptive but also non-nociceptive dorsal horn units, suggesting that tissue injury caused by s.c. formalin results in vigorous injury discharges of peripheral nerve terminals, which subsequently leads to activation of primary afferent neurons and secondary dorsal horn neurons.
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  • 20
    ISSN: 1432-1106
    Keywords: Key words Ultrastructure ; Immunohistochemistry ; Bouton ; Synaptic input ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The dendritic tree constitutes more than 93% of the receptive membrane area of a spinal motoneuron, yet little is known about its synaptic inputs. In this study we examined the distribution of glutamate-, GABA- and glycine-like immunoreactivity in boutons apposing dendrites in the L7 spinal cord motor nucleus, by use of postembedding immunohistochemistry on serial sections. We examined 799 boutons apposing 401 cross-sectioned dendrites of different calibre (range 0.2–15 µm), and 14 first-order (stem) dendrites. Thirty-five percent (35%) of the boutons were immunopositive for glutamate and 59% for GABA and/or glycine. Among the latter, 30% showed glycine immunoreactivity only and 24% were immunoreactive for both GABA and glycine. Very few were immunoreactive only for GABA (5%). As few as 6% of the boutons were judged as not enriched for any amino acid analysed. The fine structural characteristics of the boutons were in accordance with previous descriptions. The sample of dendrites was arranged in calibre bins in order to facilitate distribution analysis. Stem dendrites differed from the other bins, with a high total bouton covering (61%) and a high bouton density. Sixty-nine percent of the membrane covering was by glycine- and/or GABA-immunoreactive boutons, whereas 18% was covered by boutons enriched in glutamate. For non-stem dendrites, bouton covering fell from 33% to 12% with decreasing calibre. However, bouton apposition length decreased in parallel, yielding a fairly uniform bouton density among dendrites of different calibre. The lack of correlation between packing density and dendrite calibre was also evident when the sample of dendrites was broken down into subsamples based on content of amino acid immunoreactivity. The latter analysis also revealed that both the relative covering and density of boutons containing inhibitory amino acids (57%; glycine and/or GABA) and glutamate (38%), respectively, did not vary systematically with dendrite calibre. Combined, the data indicate that in non-stem dendrites the proportion of excitatory and inhibition inputs does not change systematically throughout the dendritic arborizations of spinal α-motoneurons. Thus, spinal motoneurons can, with respect to the general synaptic architecture, be divided into two main compartments, i.e. the proximal soma-juxtasomatic compartment (including stem dendrites) and the distal dendritc compartment. The proximal domain is under a powerful glycine and/or GABA influence. Finally, based on the data presented here and previously published data, it was calculated that spinal α-motoneurons receive in the range of 50–140×103 synaptic boutons.
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  • 21
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    Experimental brain research 119 (1998), S. 39-46 
    ISSN: 1432-1106
    Keywords: Key words Spinal cord ; Spinocervical tract ; Interneurones ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The possibility of collateral segmental actions of spinocervical tract (SCT) neurones upon interneurones with input from cutaneous and group II muscle afferents was investigated in deeply anaesthetized cats. To this end, intracellular and/or extracellular recordings were made from 35 dorsal horn and 15 intermediate zone interneurones in midlumbar segments of the spinal cord and effects of stimulation of the ipsilateral dorso-lateral funiculus (DLF) at C3 and C1 levels, i.e. below and above the lateral cervical nucleus where axons of SCT cells terminate, were compared. The stimuli applied at the C3 segment were within the range of stimuli (50–100 μA) required for antidromic activation of SCT neurones in the same experiment. Those applied at the C1 segment (200–500 μA) were at least 3 times stronger than C3 stimuli. Under the same experimental conditions, long ascending and descending tract neurones (dorsal spino-cerebellar and rubro-spinal tract neurones) with axons in the DLF were activated at similar thresholds from the C1 and C3 segments. Intracellular recordings were made from 29 interneurnoes of which 19 (65%) were dorsal horn and 10 (35%) were intermediate zone interneurones. Excitatory postsynaptic potentials (EPSPs) evoked by single stimuli applied at the C3 segment, but not the C1 segment, were found in 14 (48%) of those interneurones; their latencies (3.0–5.7 ms) and frequency following with only minimal temporal facilitation were as required for potentials being evoked monosynaptically by the fastest conducting SCT neurones. Extracellular recordings were made from 30 interneurones (24 dorsal horn and 6 intermediate zone interneurones), and in these neurones spike potentials induced from the C3, but not from the C1 segment, were evoked only by short trains of stimuli. However, their latencies from the first effective stimulus (4.3–5.4 ms) were compatible with mono- or oligosynaptically mediated collateral actions of SCT neurones. They were found in 10 (33%) of the 30 investigated interneurones. Similar effects of C3 stimuli were found in similar proportions of dorsal horn interneurones and intermediate zone interneurones. Indications were also found for synaptic actions evoked by C3 stimuli that could not be attributed to direct collateral actions of SCT neurones. In some intracellularly recorded dorsal horn interneurones, short-latency EPSPs were evoked from the C3 segment by the 2nd or 3rd stimulus in the train, but not by single stimuli. In other dorsal horn and intermediate zone interneurones, inhibitory postsynaptic potentials (IPSPs) were evoked from the C3 segment at minimal latencies (2.7–3.2 ms), which might be too short to allow their mediation via SCT neurones. We conclude that SCT neurones might be used to forward information from muscle group II and cutaneous afferents not only to neurones in the lateral cervical nucleus and via them to thalamus and cerebral cortex but also to interneurones in spinal reflex pathways. Thereby reflex actions evoked from group II and cutaneous afferents might be co-ordinated with responses mediated by supraspinal neurones. We conclude also that dorsal horn and intermediate zone mid-lumbar interneurones might contribute to the previously reported di-and poly-synaptic excitation or inhibition of postsynaptic dorsal column (PSDC), spinothalamic tract (STT) and spinomesencephalic tract (SMT) neurones by collateral actions of SCT cells. Thereby these interneurones might contribute to the co-ordination of responses mediated by various populations of supraspinal neurones.
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  • 22
    ISSN: 1432-1106
    Keywords: Key words Cortical microcircuits ; Relative modulation ; Push-pull mechanism ; Simple cell ; Cascaded inhibition ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The robust behavior, the degree of response linearity, and the aspect of contrast gain control in visual cortical simple cells are (amongst others) the result of the interplay between excitatory and inhibitory afferent and intracortical connections. The goal of this study was to suggest a simple intracortical connection pattern, which could also play a role in other cortical substructures, in order to generically obtain these desired effects within large physiological parameter ranges. To this end we explored the degree of linearity of spatial summation in visual simple cells experimentally and in different models based on half-wave rectifying cells (’’push-pull models’’). Visual cortical push-pull connection schemes originated from antagonistic motor-control models. Thus, this model class is widely applicable but normally requires a rather specific design. On the other hand we showed that a more generic version of a push-pull model, the so-called cascaded inhibitory intracortical connection scheme, which we implemented in a biologically realistic simulation, naturally explains much of the experimental data. We investigated the influence of the afferent and intracortical connection structure on the measured linearity of spatial summation in simple cells. The analysis made use of the relative modulation measure, which is easy to apply but is limited to moving sinusoidal grating stimuli. We introduced two basic push-pull models, where the order of threshold nonlinearity and linear summation is reversed. Very little difference is observed with the relative modulation measure for these models. Alterative models, like half-wave squaring models, were also briefly discussed. Of all model parameters, the ratio of excitation to inhibition in the simple cell exerts the most crucial influence on the relative modulation. Linearity deteriorates as soon as excitatory and inhibitory inputs are imbalanced and the relative modulation drops. This prediction was tested experimentally by extracellular recordings from cat area 17 simple cells and we found that about 62% showed a significant deviation from linear behavior. The problem that individual basic push-pull models are hard to distinguish experimentally led us to suggest a different solution. In order to generically account for the observed behavior (e.g., imbalance of excitation versus inhibition), we suggested a rather generic version of a push-pull model where it no longer mattered about (the hard-to-distinguish) fine differences in connectivity. Thus, we introduced a new class of biophysically realistic models (’’cascaded inhibition’’). This model class requires very little connection specificity and is therefore highly robust against parameter variations. Up to 25 cells are connected to each target cell. Thereby a highly interconnected network is generated, which also leads to disinhibition at some parts of an individual receptive field. We showed that the performance of these models simulates the degree of linearity and its variability in recal simple cells with comparatively high accuracy. This behavior can be explained by the self-regulating properties of a cascaded inhibitory connection scheme by which the balance between excitation and inhibition at a given cell is improved by the joint network effects. The virtues and the generic design of this connection pattern, therefore, allow to speculate that it is used also in other parts of the cortex.
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  • 23
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    Experimental brain research 122 (1998), S. 339-350 
    ISSN: 1432-1106
    Keywords: Key words Fictive locomotion ; Proprioception ; Flexor reflex ; Spinal cord ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The generation of locomotor-like spinal rhythms has been proposed to involve two neural centres with mutual reciprocal inhibition (Graham Brown’s ”half-centre” hypothesis). Much later a particular set of segmental flexor reflex pathways were described as being organized in accordance with this half-centre hypothesis. As these pathways became operative following injection of monoaminoxidase inhibitors and l-3,4-dihydroxyphenylalanine (l-dopa), i.e. under the same conditions under which a spontaneous locomotor activity may develop, it was assumed that these particular pathways and spinal rhythm generators involve the same neuronal networks. In order to give further evidence to this hypothesis, we investigated whether short trains to ”flexor reflex afferents” (FRA) reset the spinal locomotor rhythm, i.e. shorten or lengthen the stimulated cycle after which the regular rhythm is resumed with step cycles of the original duration. The experiments were performed in anaemically decapitated, high-spinal curarized cats. A steady locomotor rhythm was induced by injection of nialamide and l-dopa and the influence of electrical stimulation (trains of 50–1000 ms) of FRA (joint, cutaneous, and group II and III muscle afferents) onto this rhythm was tested. Stimulation of FRA induced a clear resetting of the locomotor rhythm, which was mainly characterized by a flexion reflex pattern: during the extension phase the extensor activity was interrupted and a flexion phase was initiated; during the late flexion phase mainly a prolongation of that phase with a variable change of the following extension phase was induced. In addition to this prevailing pattern, stimulation of some nerves (in particular nerves to more distal extensors and the sural nerve) could often prolong extension, when stimulated during the late extension, or terminate the flexor burst and initiate a new extension phase, when stimulated during the late flexion phase. This pattern is probably due to the concomitant stimulation of group I afferents in the case of the muscle nerves and to separate non-FRA pathways in the case of the sural nerve. The results demonstrate that the interneurones of the FRA pathways, which are operative during l-dopa-induced locomotion in spinal animals, can be considered as neuronal elements of the rhythm-generating network for locomotion.
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  • 24
    ISSN: 1432-1106
    Keywords: Key words Motor nucleus ; EMG ; Muscle architecture ; Muscle fiber ; Caudofemoralis ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Feline caudofemoralis (CF) is a promising preparation in which to study the properties of mammalian fast-twitch skeletal muscle, but little is known about its muscle fiber properties, architecture, and motor innervation. We used histochemical techniques to confirm that it contained predominantly type IIB fibers (95±2%, n=8, with six of eight muscles composed exclusively of type IIA and IIB fibers), but physiological experiments showed less fatiguability than for the type IIB component of medial gastrocnemius. This may be related to the surprisingly strong and regular recruitment of CF during repetitive tasks such as walking and trotting, which we demonstrated electromyographically. We measured muscle length over the anatomical range of motion for CF (∼0.6–1.2 L 0) and estimated working length during walking and trotting (∼0.95–1.15 L 0). The specific tension was similar to that of the exclusively slow-twitch soleus muscle (31.2±4.7 N/cm2 compared with 31.8±4.1 N/cm2; P〉0.8). Single fiber dissections of CF revealed a series-fibered architecture with a mean of 2.3 fibers, each 2.5 cm long, required to span the fascicle length. We identified two neuromuscular compartments in CF by cutting one of the two nerve branches innervating CF and depleting the glycogen stores in the intact motor units. These compartments were in parallel and extended the length of the muscle; their electromyographic activity was similar during various natural behaviors. CF and gluteus maximus motoneurons were labeled concurrently with a combination of fluorescent, retrograde tracers including Fluororuby, Fluorogold and Fast Blue. The CF motor nucleus was located in L7-S1, overlapping and intermingling extensively with the nucleus of the adjacent gluteus maximus muscle. Distributions of CF motoneuron diameter revealed one large peak around 50–55 µm, with relatively few small-diameter (less than 35 µm) cells. Using estimates of the total number of fibers in three muscles and the estimated number of α-motoneurons for those same muscles, we calculated a mean innervation ratio of ∼270, which is at the low end of the innervation ratios for type IIB motor units from other feline muscles and more similar to type IIA motor units. In general, CF appears to be a useful preparation in which to study the properties of fast-twitch muscle, but these properties may vary somewhat from type IIB fibers from different muscles.
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  • 25
    ISSN: 1432-1106
    Keywords: Key words Spinal inhibition ; Interneurons ; Micturition ; Bladder-sphincter dyssynergia ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Micturition in the decerebrate cat is characterized by a coordinated bladder contraction and a simultaneous decrease in external urethral sphincter (EUS) efferent activity. Without the suppression of EUS activity, voiding is significantly impaired, resulting in a state sometimes referred to as bladder-sphincter dyssynergia. The aim of the present study was to determine whether glycinergic inhibition contributes to the suppression of EUS activity during micturition evoked by bladder distension or electrical stimulation of the pontine micturition center (PMC) in decerebrate cats. Using subconvulsive intravenous doses of strychnine (0.1–0.24 mg/kg), we examined changes in bladder and EUS electroneurographic (ENG) activity during micturition. Following subconvulsive doses of strychnine, tonic EUS ENG activity increased during bladder filling in five of six animals. In the presence of strychnine, it was possible to evoke reflex bladder contractions of similar duration and peak pressure to those observed before strychnine administration. However, there was an absence of suppression of EUS ENG activity during the bladder contractions in all the animals. To determine whether the changes in sphincter activity could be due to strychnine acting at glycine receptors on EUS motoneurons, sacral spinal tissue was processed for a structural protein (gephyrin) associated with the glycine receptor. Motoneurons in Onuf′s nucleus in S1 were identified using choline acetyltransferase immunohistochemistry and subsequently processed with a gephyrin monoclonal antibody. Abundant gephyrin labeling was evident throughout Onuf′s nucleus. Since Onuf′s nucleus is made up of EUS and other motoneuron populations, a sample of antidromically identified urethral and anal sphincter motoneurons were intracellularly labeled with tetramethylrhodamine dextran (TMR-D) and then processed with the gephyrin antibody. Using dual-beam confocal microscopy, gephyrin immunoreactivity was observed on the soma and proximal processes of individual EUS motoneurons in both male and female animals. It was concluded that a strychnine-sensitive mechanism contributes to the suppression of sphincter activity normally observed during voiding. Although glycinergic inhibition may affect several components of the circuitry responsible for micturition, it appears that the suppression of EUS motoneurons during micturition may be partly due to a direct glycinergic inhibition of the EUS motoneurons.
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  • 26
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    Experimental brain research 119 (1998), S. 315-323 
    ISSN: 1432-1106
    Keywords: Key words Stance posture ; Balance ; Epaxial muscles ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  This study examined the role of trunk extensor muscles in the thoracic and lumbar regions during postural adjustments in the freely standing cat. The epaxial extensor muscles participate in the rapid postural responses evoked by horizontal translation of the support surface. The muscles segregate into two regional groups separated by a short transition zone, according to the spatial pattern of the electromyographic (EMG) responses. The upper thoracic muscles (T5-9) respond best to posteriorly directed translations, whereas the lumbar muscles (T13 to L7) respond best to anterior translations. The transition group muscles (T10-12) respond to almost all translations. Muscles group according to vertebral level rather than muscle species. The upper thoracic muscles change little in their response with changes in stance distance (fore-hindpaw separation) and may act to stabilize the intervertebral angles of the thoracic curvature. Activity in the lumbar muscles increases along with upward rotation of the pelvis (iliac crest) as stance distance decreases. Lumbar muscles appear to stabilize the pelvis with respect to the lumbar vertebrae (L7-sacral joint). The transition zone muscles display a change in spatial tuning with stance distance, responding to many directions of translation at short distances and focusing to respond best to contralateral translations at the long stance distance.
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  • 27
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    Experimental brain research 119 (1998), S. 324-332 
    ISSN: 1432-1106
    Keywords: Key words Vertebral column ; Antigravity support ; Scapula ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  This study examined the configuration of the vertebral column of the cat during independent stance and in various flexed positions. The range of motion in the sagittal plane is similar across most thoracic and lumbar joints, with the exception of a lesser range at the transition region from thoracic-type to lumbar-type vertebrae. The upper thoracic column exhibits most of its range in dorsiflexion and the lower thoracic and lumbar in ventroflexion. Lateral flexion is limited to less than 5° at all segments. The range in torsion is almost 180° and occurs primarily in the midthoracic region, T4-T11. Contrary to the depiction in most atlases, the standing cat exhibits several curvatures, including a mild dorsiflexion in the lower lumbar segments, a marked ventroflexion in the lower thoracic and upper lumbar segments, and a profound dorsiflexion in the upper thoracic (above T9) and cervical segments. The curvatures are not significantly changed by altering stance distance but are affected by head posture. During stance, the top of the scapula lies well above the spines of the thoracic vertebrae, and the glenohumeral joint is just below the bodies of vertebrae T3-T5. Using a simple static model of the vertebral column in the sagittal plane, it was estimated that the bending moment due to gravity is bimodal with a dorsiflexion moment in the lower thoracic and lumbar region and a ventroflexion moment in the upper thoracic and cervical region. Given the bending moments and the position of the scapula during stance, it is proposed that two groups of scapular muscles provide the major antigravity support for the head and anterior trunk. Levator scapulae and serratus ventralis form the lateral group, inserting on the lateral processes of cervical vertebrae and on the ribs. The major and minor rhomboids form the medial group, inserting on the spinous tips of vertebrae from C4 to T4. It is also proposed that the hypaxial muscles, psoas major, minor, and quadratus lumborum could support the lumbar trunk during stance.
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  • 28
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    Experimental brain research 119 (1998), S. 333-344 
    ISSN: 1432-1106
    Keywords: Key words Disparity sensitivity ; Binocular interactions ; Superior colliculus ; Stereopsis ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Cells in the superficial layers of the superior colliculus of the cat have mainly binocular receptive fields. The aim of the present experiment was to investigate the sensitivity of these cells to horizontal spatial disparity. Unit recordings were carried out in the superficial layers of the superior colliculus of paralyzed and anesthetized cats. Centrally located receptive fields were mapped, separated using prisms, and then stimulated simultaneously using two luminous bars optimally adjusted to the size of the excitatory region of the receptive fields. Only binocular cells were tested, and 65% of these units were found to be sensitive to spatial disparities. Some cells (20%) were clearly insensitive to spatial disparity and the remaining 15% showed complex, unclassifiable interactions. The sensitive cells could be divided into four classes based on their disparity-sensitivity profiles: 38% showed excitatory interactions, whereas 9% showed inhibitory interactions. Moreover, 11% and 7% of the cells responded, respectively, to crossed or uncrossed disparities, and were classified as near cells and far cells. Whereas the general shapes of the sensitivity profiles were similar to those of cells in areas 17–18, selectivity in the superior colliculus was significantly coarser. The superficial layers of the superior colliculus project topographically to the deep layers of the superior colliculus, which are known to contain circuits involved in the control of ocular movements. The results thus suggest that disparity-sensitive cells of the superior colliculus could feed information to these oculomotor neurons, allowing for the localization and fixation of objects on the appropriate plane of vision.
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  • 29
    ISSN: 1432-1106
    Keywords: Key words Antagonist neck muscles ; Eye movements ; Unilateral vestibular neurectomy ; Visual substitution ; Motor strategies ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The purpose of this study was to investigate changes in neck muscle and eye movement responses during the early stages of vestibular compensation (first 3 weeks after unilateral vestibular neurectomy, UVN). Electromyographic (EMG) activity from antagonist neck extensor (splenius capitis) and flexor (longus capitis) muscles and eye movements were recorded during sinusoidal visual and/or otolith vertical linear stimulations in the 0.05–1 Hz frequency range (corresponding acceleration range 0.003–1.16 g) in the head-fixed alert cat. Preoperative EMG activity from the splenius and longus capitis muscles showed a pattern of alternate activation of the antagonist neck muscles in all the cats. After UVN, two motor strategies were observed. For three of the seven cats, the temporal activation of the individual neck muscles was the same as that recorded before UVN. For the other four cats, UVN resulted in a pattern of coactivation of the flexor and extensor neck muscles because of a phase change of the splenius capitis. In both subgroups, the response patterns of the antagonist neck muscles were consistent for each cat independently of the experimental conditions, throughout the 3 weeks of testing. Cats displaying alternate activation of antagonist neck muscles showed an enhanced gain of the visually induced neck responses, particularly in the high range of stimulus frequency, and a gain decrease in the otolith-induced neck responses at the lowest frequency (0.25 Hz) only. By contrast, for cats with neck muscle coactivation, the gain of the visually induced neck responses was basically unaffected relative to preoperative values, whereas otolith-induced neck responses were considerably decreased in the whole range of stimulation. As concerns oculomotor responses, results in the two subgroups of cats were similar. The optokinetic responses were not affected by the vestibular lesion. On the contrary, otolith-induced eye responses showed a gain reduction and a phase lead. Deficits and short-term changes after UVN of otolith- and semicircular canal-evoked collic and ocular responses are compared.
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  • 30
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    European radiology 8 (1998), S. 849-857 
    ISSN: 1432-1084
    Keywords: Key words: Ultrasound ; Physics ; Vascular studies ; Vascular pathologies ; Ultrasonic contrast agents ; Clinical applications
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract. The choice of the optimal ultrasonic frequency for vascular studies is determined by the required resolution and penetration. Anatomical real-time two-dimensional imaging and blood flow studies provide complementary information. Intravascular scanning allows high-frequency ultrasound to be used, with correspondingly good spatial resolution. Contrast resolution is degraded by beam side lobes and the limited dynamic range of the ultrasonic pulse. The physics of ultrasonic scattering by blood, pulsed Doppler and duplex scanning and colour flow imaging performances determines the limits of clinical applications. Contrast agents enhance the echogenicity of blood, improving sensitivity and, through second harmonic detection, suppressing solid tissue echoes. Three-dimensional display, with segmentation by the presence of the flow signal, facilitates spatial perception. Clinical applications in vascular pathologies are summarised.
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  • 31
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    Experimental brain research 121 (1998), S. 319-333 
    ISSN: 1432-1106
    Keywords: Key words Spinal cord ; Synaptic inhibition ; GABAA receptors ; GABAB receptors ; GABA antagonists ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  In pentobarbitone-anaesthetised spinal cats, a comparison was made of the effects of intravenous bicuculline hydrochloride, a GABAA-receptor antagonist, and several (-)-baclofen (GABAB-receptor) antagonists (CGP 35348, 46381, 56999A) on the prolonged inhibition of extensor-muscle monosynaptic reflexes, recorded from lumbar ventral roots, by brief or continuous tetanic stimulation of low-threshold afferent fibres of hindlimb flexor muscles. Two components of brief tetanus inhibition were detected. Whilst possibly of similar central latency, the inhibition associated with GABAB receptors had a longer time course than that reduced by bicuculline. Furthermore, whereas bicuculline reduced primary afferent depolarization, generated by the inhibitory volleys, and detected as dorsal-root potentials, such potentials were generally enhanced by intravenous baclofen antagonists. The inhibition of reflexes during and after continuous (333 Hz) tetanic flexor-nerve stimulation appeared to be predominantly associated with the activation of GABAB receptors. In the period following continuous tetanic flexor-nerve stimulation, during which monosynaptic extensor reflexes were reduced in amplitude, the action potentials of the intraspinal terminations of extensor-muscle group-Ia afferent fibres were reduced in duration, as detected by the time course of the recovery of the threshold to extracellular microstimulation following the arrival of an orthodromic impulse. A reduction in termination action-potential duration also accompanied the reduction by microelectrophoretic (-)-baclofen of the release of excitatory transmitter from group-Ia terminations, both presynaptic effects being blocked by microelectrophoretic baclofen antagonists. However, the reduction of the duration of the action potential of individual group-Ia terminations, which followed continuous flexor-nerve stimulation, was not sensitive to the baclofen antagonist CGP 55845A, but was diminished by bicuculline methochloride. Intravenously administered bicuculline hydrochloride, however, had little or no effect on the inhibition of reflexes following continuous flexor-nerve stimulation. These observations are discussed in the context of possible intraspinal pathways and pre- and postsynaptic mechanisms for GABAA and GABAB receptor-mediated inhibition of the monosynaptic excitation of spinal motoneurones and of the functional significance of central GABAB receptor-associated inhibitory processes, given the relatively minimal effects on motor activity and behaviour produced by baclofen antagonists that penetrate the mammalian blood-brain barrier.
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  • 32
    ISSN: 1432-2072
    Keywords: Key words Retrorubral nucleus ; A8 ; Oro-facial dyskinesia ; Striatum ; GABA ; Bicuculline ; Muscimol ; DPI (3 ; 4 dihydroxy-phenylimino)-2-imidazoline ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Orofacial dyskinesia (OFD) is a disorder characterized by involuntary movements of the oral and facial muscles. OFD attacks can be elicited acutely in cats by local injections of dopaminergic agents into the anterodorsal part (r-CRM) of the caudate nucleus. Because the dopaminergic A8 cell group, being embedded in the retrorubral nucleus (RRN), gives rise to fibres which terminate in the r-CRM, two questions arose: (1) whether the A8 cell group forms part of the circuitry that directs and/or modulates OFD, and (2) whether GABA-ergic compounds in the RRN play a role in OFD, and if so, whether a pharmacological GABA-ergic intervention of the activity in the RRN modulates or mediates OFD. For this purpose, the activity of the RRN was manipulated with local injections of the GABAA agonist muscimol and antagonist bicuculline. These local injections into the RRN were subsequently combined with manipulations of dopamine transmission in the r-CRM with local injections of the selective DAi receptor agonist (3,4-dihydroxyphenylimino)-2-imidazoline. The present study shows that local injections of GABA-ergic compounds into the RRN do not elicit OFD attacks in cats, but can modulate oral behaviour elicited from the r-CRM. The latter effect is dose dependent and GABA-ergic specific.
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  • 33
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    Cell & tissue research 293 (1998), S. 285-291 
    ISSN: 1432-0878
    Keywords: Key words Muscle ; Masseter ; Biceps ; P blood group ; CD77 ; Galactose ; Cat ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  There is evidence that glycans carrying terminal galactose residues are differently expressed in the sarcoplasm of different muscle fiber types. In this study monoclonal antibodies directed against P blood group antigens Pk: Galα1–4Galβ1–4Glcβ- and P1: Galα1–4Galβ1–4GlcNAcβ- were used to detect terminal α-galactosylated glycoconjugates on muscle proteins. Electrotransfer of proteins, extracted from human masseter and biceps muscles, to nitrocellulose after polyacrylamide gel electrophoresis (PAGE) and incubation with anti-Pk (CD77) consistently showed two bands with apparent molecular weights of 66 kDa and 64 kDa. In fresh frozen muscle sections from some humans there was endothelial reaction with anti-CD77 in capillaries, venules and veins but not in arterioles and arteries. In muscle samples from other humans there was no staining of endothelial cells. Formalin-fixed human muscle displayed a CD77 reaction with highest accumulation of reaction product at the periphery of the fibers. This may be explained by the presence of Pk glycoconjugates on intermediate filaments in muscle fibers. In preparations of cat masseter muscle proteins the antibodies against P1Pk antigens reacted with a 170 kDa and a 55 kDa band while in preparations of cat biceps brachii only a 55 kDa band was reactive. The specificities of the antibodies were investigated by fluorescence-activated cell sorter (FACS), α- and β-galactosidase digestion and inhibitory sugars. This study indicates that glycans carrying Galα1–4Galβ1- epitopes are expressed on myofibrillar associated proteins.
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  • 34
    ISSN: 1573-899X
    Keywords: Cat ; striate cortex ; internal connections ; horseradish peroxidase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Studies were carried out on the organization of the internal connections of the striate cortex in cats in the projection zone of the center (0–5°) of the field of vision by microintophoretic application of horseradish peroxidase to electrophysiologically identified orientational columns. The area containing neurons showing retrograde labeling in most cases extended in the mediolateral direction. Labeled cells were located in the upper (II, III) and lower (V, VI) layers of the cortex, and the shapes and orientations of the areas containing labeled neurons in these layers coincided. Spatial asymmetry was detected in the distribution of labeled neurons relative to the orientational column studied. Labeled cells were located predominantly medial to the columns, regardless of the distance from the projection of the area centralis. Considering the visuotopical map of field 17, the asymmetry detected here provides evidence that neurons in orientational columns have more extensive connections with neurons of the peripheral part of the cortex. An asymmetrical distribution of “silent” zones around the receptive fields of neurons in orientational columns is suggested, and that these appear to receive influences from the periphery of the visual field.
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  • 35
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1025-1035 
    ISSN: 0887-6266
    Keywords: polymer thin films ; thermosets ; microelectronics ; moisture ; physical aging ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In polymers for microelectronics applications, moisture is known to have a deleterious effect upon device reliability. In this paper, the moisture transport behaviors of a newly developed family of all-aromatic and aromatic/aliphatic copolyester thermosetting films were described. The moisture uptake as a function of temperature, relative humidity, sample thickness, and processing conditions were presented via conjugate moisture sorption tests.1 It was found that the post curing near but below Tg resulted in an increase in both total moisture uptake and diffusion coefficient due to the effect of physical aging and the generation of sample defect volume. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1025-1035, 1998
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  • 36
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1061-1080 
    ISSN: 0887-6266
    Keywords: polymer blends ; dilatometry ; free volume ; specific volume ; excess volume ; compressibility ; thermal expansivity ; equation of state ; scaling parameters ; crystallinity ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-miscible polymer blends of poly(ethylene oxide)/atactic poly(methyl methacrylate (PEO/a-PMMA)) were prepared by melt-mixing and characterized by pressure-volume-temperature (PVT) dilatometry in the pressure and temperature range of 0 to 200 MPa and 20 to 200°C, respectively. The PVT data were analyzed in terms of two equations of state (EOS). The empirical Tait EOS was applied in the glassy, semicrystalline, and equilibrium melt state, and the Simha-Somcynsky EOS theory was applied in the equilibrium melt and glassy state. The Simha-Somcynsky EOS theory contains a free volume function. The temperature, pressure, and composition dependence of the free volume fraction h calculated from the Simha-Somcynsky EOS theory was studied. As a function of blend composition we observe that the free volume fraction, thermal expansivity, and compressibility all deviate mainly positively from linearity while the specific volume deviates mainly negatively from linearity. These findings are reconciled with composition-dependent free volume parameters, the free volume and cell volume as well as with self- and cross-interaction parameters derived from the Simha-Somcynsky EOS theory as applied to polymer mixtures. Moreover, the pressure dependence of glass and melting transitions as well as crystallization kinetics have been investigated. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1061-1080, 1998
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  • 37
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1201-1209 
    ISSN: 0887-6266
    Keywords: polymer electrolytes ; NMR ; conductivity ; glasses ; Arrhenius and VTF dependences ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have studied the temperature variation of conductivity and 1H NMR linewidth of (PEG)xNH4ClO4 (x = 20, 30, 46, 100, 200, & 1000) polymer electrolyte systems. The temperature dependence of the conductivity shows two distinct behaviors, the low temperature VTF dependence crossing over to Arrhenius dependence at higher temperatures. The departure from the VTF behavior is found to be composition dependent. NMR spectra indicate the presence of large fractions of crystalline regions that start to melt around the crossover temperature. We understand the deviation from the VTF behavior as a consequence of this crystalline to elastomer transition. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1201-1209, 1998
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  • 38
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1227-1233 
    ISSN: 0887-6266
    Keywords: FTIR spectroscopy ; isotactic polystyrene ; crystallization process ; induction period ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt crystallization process of isotactic polystyrene (i-PS) was studied by means of in situ Fourier transform infrared (FTIR) spectroscopy, with a focus on the conformational changes during the induction period. The spectra obtained during the induction period suggested the occurrence of some ordered structure that is characterized by higher regularity and packing of the helical moieties than observed in the melt. This ordered structure was clearly different from the amorphous structure, and close to the crystal structure. The Avrami analysis indicated that the formation process of the ordered structure at the late stage of the induction period is similar to the growth process of the crystallites after the induction period. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1227-1233, 1998
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  • 39
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 237-251 
    ISSN: 0887-6266
    Keywords: segmented ; polyurethanes ; crosslinked ; mechanical ; dielectric properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical and dielectric properties of two series of segmented polyurethanes having soft segment concentration of 50 and 70% and a varying degree of crosslinking through the hard segment were studied. The degree of crosslinking in each series was varied by varying the butane diol/trimethylol propane ratio in the chain extender mixture. Tensile strength, elongation at break decrease, but elastic recovery increases monotonically with increasing crosslinking. The plateau modulus in the dynamic mechanical test decreases and then increases with increasing TMP content. Crosslinking causes broadening of the soft segment glass transition as seen by permittivity and loss factor measurements. It also affects high temperature behavior (above the glass transition of the hard segment); it lowers permittivity, loss factor, and ionic conductivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 237-251, 1998
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  • 40
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2379-2391 
    ISSN: 0887-6266
    Keywords: block copolymer ; thermoplastic elastomer ; physical gel ; polymer micelle ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoplastic elastomer gels (TPEGs) composed of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and a low-volatility, midblock-compatible mineral oil have been investigated at different oil concentrations to ascertain the effect of composition on TPEG morphology and mechanical properties. The impact of thermal processing is also examined by comparing gels thermally quenched to 0°C or slowly cooled to ambient temperature. Transmission electron micrographs reveal that gels with 70 to 90 wt % oil exhibit styrenic micelles measuring ca. 24 nm in diameter. Variation in composition or cooling rate does not have any perceivable effect on micelle size or shape, whereas the rate at which the gels are cooled influences the extent of microstructural order and the time to rupture (tR) at constant strain. Dynamic rheological testing confirms the presence of a physically crosslinked network at TPEG compositions ranging from 70 to 90 wt % oil, independent of cooling rate. Results presented here suggest that the dynamic elastic shear modulus (G′) scales as tαR where α varies from 0.41 to 0.59, depending on cooling rate. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2379-2391, 1998
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  • 41
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2423-2433 
    ISSN: 0887-6266
    Keywords: gelation theory ; nonlinear polymerization ; nonrandom crosslinking ; molecular weight distribution ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On the basis of the first-order Markovian statistics, we propose a general matrix formula for the weight-average molecular weight of crosslinked polymer systems, explicitly given by M̄w = M̄w,0 + WX0 (I - X)-1 Sf. This equation is valid for both step and chain-growth polymerizations, including those in a nonequilibrium state irrespective of the reactor types used. In the context of the present theory, the onset of gelation is simply stated as a point at which the largest eigenvalue of the matrix X reaches unity (i.e., det(I - X) = 0). The present theory provides a unified point of view for various types of gelling systems. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2423-2433, 1998
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  • 42
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 555-565 
    ISSN: 0887-6266
    Keywords: polyester ; annealing ; birefringence ; mechanical loss factor ; orientation ; density ; crystalline ; profile ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyester (Egyptian) fibers were annealed at constant temperature (190°C) with different annealing times. Density, crystallinity, mean square density fluctuation, mechanical loss factor, and molecular orientation were calculated. Densities and mechanical loss factor were determined using an acoustic method. Changes in the molecular orientation were evaluated from the resulting optical data using the polarizing Pluta interference microscope. Correlation of data obtained by one method with another leads to relational changes in optothermal properties and in the molecular orientation. Changes of refractive index profiles of annealed PET fibers are provided. Illustrations using graphs and microinterferograms are shown. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 555-565, 1998
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  • 43
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 595-606 
    ISSN: 0887-6266
    Keywords: IR ; perfluoro(sulfonate/carboxylate) bilayer ; sol-gel reactions ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: [Perfluoro-organic]/[silicon oxide] hybrids were formed by conducting sol-gel reactions of tetraethylorthosilicate within a perfluoro(carboxylate/sulfonate) bilayer membrane in the Co+2 form. FTIR and 29Si solid-state NMR spectroscopies were used to probe general aspects of molecular structure within the silicon oxide phase as a function of its relative content. The internal gel structure is considerably unconnected in terms of the population of Si—O—Si groups in cyclic vs. linear substructures and degree of Si atom coordination about bonded SiO4 units. In situ (HO)xSiO2[1-1/4x] intrastructure become increasingly less connected and more strained with regard to bonding geometry with increasing percent silicon oxide. Structural differences are seen between the silicon oxide component incorporated in carboxylate and sulfonate layers. These inorganically modified perfluorinated ionomers have potential as fast-proton conducting membranes for fuel cells and as permselective membranes in liquid pervaporation cells. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 595-606, 1998
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  • 44
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 607-615 
    ISSN: 0887-6266
    Keywords: ternary phase diagram ; binodal curve ; Flory-Huggins theory ; interaction parameter ; membrane formation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this work, the ternary phase diagrams in three nonsolvent/solvent/PMMA systems (n-hexane/n-butyl acetate/PMMA, water/acetone/PMMA, and n-hexane/acetone/PMMA) were constructed by theoretical calculation and experimental measurement. Binodal curves were calculated by using the Flory-Huggins theory for three-component systems and measured by titrating the PMMA solution with nonsolvent until the onset of turbidity. By using concentration-dependent nonsolvent/solvent and solvent/PMMA interaction parameters and constant nonsolvent/PMMA interaction parameters, good agreement has been obtained between the calculation and the measurement. The values of nonsolvent/solvent interaction parameters were taken from the literature sources, and the values of solvent/PMMA and nonsolvent/PMMA interaction parameters were measured by vapor sorption and swelling equilibrium, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 607-615, 1998
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  • 45
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 143-154 
    ISSN: 0887-6266
    Keywords: polymer simulation ; stress relaxation ; molecular dynamics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have been developing a physical picture on the atomic level of stress relaxation in polymer melts by means of computer simulation of the process in model systems. In this article we treat a melt of freely jointed chains, each with N = 200 bonds and with excluded-volume interactions between all nonbonded atoms, that has been subjected to an initial constant-volume uniaxial extension. We consider both the stress relaxation history σ(t) based on atomic interactions, and the stress history σe(t; NR) based on subdividing the chain into segments with NR bonds each, with each segment regarded as an entropic spring. It is found that at early times σ(t) 〉 σe(t; NR) for all NR, and that, for the remainder of the simulation, there is no value of NR for which σ(t) = σe(t; NR) for an extended period; by the end of the simulation σ(t) has fallen just below the value σe(t; 50). The decay of segment orientation, 〈P2(t; NR)〉, and of bond orientation 〈P2(t; 1)〉, is computed during the simulation. It is found that the decay of the atom-based stress σ(t) is closely related to that of 〈P2(t; 1)〉. This result may be understood through the concept of steric shielding. The change in local structure of the polymer melt during relaxation is also studied. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 143-154, 1998
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  • 46
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 181-190 
    ISSN: 0887-6266
    Keywords: dynamics ; rigid-rod ; semidilute ; birefringence ; rotational diffusivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamics of rigid-rod-like molecules are studied using rheo-optical techniques. Measurements of flow birefringence as a function of shear rate are utilized to understand the scaling behavior of rotational diffusivity with respect to concentration and temperature. The concentration scaling exponent increases with increasing concentration and the scaling laws are valid in narrow concentration windows. The Doi-Edwards (DE) scaling law Dr ∼ c-2, holds at very high concentrations (cL3 〉 150). The concentration scaling exponent decreases dramatically with increasing temperature at concentrations, cL2d 〉 1. Scaling of rotational diffusivity, with respect to temperature and solvent viscosity in the semidilute regime, does not follow the predictions of DE theory (and related caging ideas). On the contrary, a model proposed by Fixman was found to explain both the temperature and concentration dependence of the rotational diffusivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 181-190, 1998
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  • 47
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 221-235 
    ISSN: 0887-6266
    Keywords: segmented ; polyurethanes ; crosslinked ; properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two series of segmented polyurethanes, one containing 50% soft segments and the other with 70% soft segments were synthesized. Chemical crosslinks were introduced through the hard segment in a controlled way. Chemical polyurethane networks were characterized by swelling. The effect of the degree of crosslinking on properties was examined. It was found that chemical crosslinks in the hard segment reduce the mobility of the soft phase and destroy the crystallinity of the hard phase, but they improve heat stability of the hard domains. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 221-235, 1998
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  • 48
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 281-288 
    ISSN: 0887-6266
    Keywords: side-chain liquid-crystalline polymer membrane ; pervaporation ; benzene/cyclohexane mixture ; state-transformation ; benzene permselectivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a benzene/cyclohexane mixture of 10 wt % benzene was permeated through side-chain liquid-crystalline polymer (LCP) membranes by pervaporation at various temperatures, the permeation rate increased with increasing permeation temperature. The LCP membranes also exhibited a benzene permselectivity. The permselectivity for the benzene/cyclohexane mixture through the LCP membrane was different in the glassy, liquid-crystalline, and isotropic states. The LCP membrane had different apparent activation energies for permeation at each state. LCP membrane in the liquid-crystalline state had the highest apparent activation energy of the three states. Results suggest that the benzene permselectivity was influenced by changes in the LCP membrane structure, i.e., a state-transformation. It was found that a balance of the orientation of mesogenic groups and the flexibility of the siloxane chains was very important for benzene permselectivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 281-288, 1998
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  • 49
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 325-335 
    ISSN: 0887-6266
    Keywords: dispersion polymerization ; styrene ; water-ethanol mixtures ; partitioning behavior ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simulation model has been developed to predict the partitioning behavior of styrene in dispersion polymerization in ethanol-water mixtures. The composition of both the continuous phase and the dispersed phase are quantitatively estimated throughout the polymerization process. The presence of water in the system causes a considerable increase of the styrene partitioning in favor of the particles. Thus, at 70°C and for an initial composition of ethanol/water/styrene = 63.3/26.9/9.8, the concentration of styrene in the particles is about 4.8 times higher than that in the serum instead of about one in pure ethanol. The higher the polymerization temperature, the lower the styrene concentration in the particles; the higher the initial styrene concentration, the higher the styrene concentration in the particles, whereas the partition coefficient is not largely effected. In contrast, neither the interfacial tension nor the final particle size do significantly alter the simulation results. The predicted data from this model have been successfully applied to clarify the mechanisms involved in dispersion polymerization, in terms of stabilization and of kinetic events. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 325-335, 1998
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  • 50
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 357-371 
    ISSN: 0887-6266
    Keywords: gelation theory ; nonlinear polymerization ; molecular weight distribution ; branched polymers ; polymer modification ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A Markovian model is proposed for nonrandom branching reactions, by using free-radical polymerization that involves chain transfer to polymer as an example. Free-radical polymerizations are kinetically controlled; therefore, each primary polymer molecule experiences different history of branched structure formation. By assuming that the primary chains with the identical birth time conform to the same chain connection probabilities, the nonlinear structural development can be viewed as a system in which the primary chains formed at different birth times are combined into nonlinear polymers in accordance with the first-order Markov chain statistics. An explicit formula for the weight-average chain length is derived in a matrix form. The onset of gelation is simply stated as a point at which the largest eigenvalue of the transition matrix X reaches unity, i.e., det(X - I) = 0. This criterion for the onset of gelation can be considered as an extension of the Flory/Stockmayer theory to a nonequilibrium reaction system. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 357-371, 1998
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  • 51
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2811-2819 
    ISSN: 0887-6266
    Keywords: PTFE/hexafluoropropylene copolymers ; crystal ; disorder ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of new copolymers of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) containing up to 50 mol % of the hexafluoropropylene comonomer have been investigated with respect to chain conformation and crystal structure using wide-angle X-ray diffraction (WAXD). Increasing HFP content leads to significant departures from the highly ordered crystalline structure of the homopolymer PTFE; the helical conformation of the chain relaxes and untwists to accommodate the larger —CF3 pendant group in the HFP unit. Simultaneously the lateral hexagonal packing of the helices becomes less ordered and the a-dimension of the hexagonal cell increases. The above effects are progressive with increasing HFP content. At 50 mol % HFP incorporation the structure is a disordered crystalline phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2811-2819, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2865-2868 
    ISSN: 0887-6266
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2877-2886 
    ISSN: 0887-6266
    Keywords: ionomers ; NIR ; chemometrics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Near Infrared (NIR) spectroscopy coupled with chemometrics techniques were utilized to study the composition and properties of styrene-sodium methacrylate ionomers. Predictive models were obtained for mol % ionic content, as well as for the ionic cluster glass transition temperature, storage modulus, and tan δ peak parameters. The results illustrate the feasibility of using NIR and chemometrics algorithms as a property predictive tool, as well as the potential for the development of full calibration models. The chemometric parameters are discussed based on correlations with ionomer NIR spectral features and the role water molecules play as a probe for the associated structure of the ionomer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2877-2886, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2905-2910 
    ISSN: 0887-6266
    Keywords: polyalkylthiophenes ; heterojunction ; BF3-diethyl ether ; electropolymerization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new kind of all-organic heterojunction consisting of polythiophene and its derivatives was prepared by the electrochemical method in the presence of boron trifluoride diethyl ether as supporting electrolyte on indium-tin oxide glass electrode. It was observed that sequential-different oxidation potential among layers of polythiophenes is a prerequisite for the heterojunction to show rectification effect. The carrier-flow of the three semiconductors for PBrT/PT/PMT heterojunction was discussed in detail. Its rectification ratio, barrier height, and ideality factor were 392 (±2 V), 0.89 eV, and 8.1, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2905-2910, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2931-2939 
    ISSN: 0887-6266
    Keywords: associations ; random copolymers ; self-diffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The self-diffusion of four styrene-methylmethacrylate random copolymers dissolved in acetone, a thermodynamically bad solvent for the styrene sequences in the copolymer, were investigated by pulsed-field gradient NMR. The echo attenuations Sinc(q,t) are dominated by diffusion of clusters. At higher concentrations, physical gelation sets in (formation of a transient network), which is manifested in an anomalous, restricted diffusion at short observation times. The measured fluctuations of the positions of the chain segments in the transient network have an amplitude of about 100 nm. The free long-range diffusion attained at long observation times shows a much stronger concentration dependence than in the nonassociating solvent benzene. The results are in accord with light-scattering investigations. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2931-2939, 1998
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  • 56
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 95-104 
    ISSN: 0887-6266
    Keywords: blends ; melting behavior ; miscibility ; FTIR ; hydrogen bond interactions ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The miscibility of poly(4-hydroxystyrene-co-methoxystyrene) (HSMS) and poly(ε-caprolactone) (PCL) was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). HSMS/PCL blends were found to be miscible in the whole composition range by detecting only a glass transition temperature (Tg), for each composition, which could be closely described by the Fox rule. The crystallinity of PCL in the blends was dependent on the Tg of the amorphous phase. The greater the HSMS content in the blends, the lower the crystallinity. The polymer-polymer interaction parameter, χ32, was calculated from melting point depression of PCL using the Nishi-Wang equation. The negative value of χ32 obtained for HSMS/PCL blends has been compared with the value of χ32 for poly(4-hydroxystyrene) (P4HS)/PCL blends. The specific nature, quantitative analysis, and average strength of the intermolecular interactions in HSMS/PCL and P4HS/PCL blends have been determined at room temperature and in the molten state by means of Fourier transform infrared spectroscopy (FTIR) measurements. The FTIR results have been in good correlation with the thermal behavior of the blends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 95-104, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 133-141 
    ISSN: 0887-6266
    Keywords: recrystallization rate ; equilibrium melting temperature ; differential scanning calorimetry (DSC) ; poly(butylene terephthalate) (PBT) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is described for measuring the heat and rate of recrystallization following partial melting. The method uses a specific sequence of temperatures with a differential scanning calorimeter, and the melting and recrystallization processes were confirmed by optical observations. The method was applied to poly(butylene terephthalate). The rate of recrystallization was found to be roughly two orders of magnitude faster than isothermal crystallization from the melt. The melting temperatures obtained from recrystallization were used in the Hoffman-Weeks equation to deduce 236°C as the equilibrium melting temperature for poly(butylene terephthalate). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 133-141, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3115-3125 
    ISSN: 0887-6266
    Keywords: interfacial thickness ; PPO ; SAN ; SMA ; neutron reflectivity NR ; binary interaction energies ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Estimates for the thickness of the interface between poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) and copolymers of styrene-acrylonitrile (SAN) and styrene-maleic anhydride (SMA) based on the theory of Helfand and Tagami are compared to neutron reflectivity (NR) measurements. Good agreement is found between the NR measurements and theoretical predictions that make use of a mean field binary interaction model and previously reported binary interaction energies. The techniques outlined in this work may be used to understand relationships between the mechanical properties of multiphase polymer blends and the fundamental thermodynamics of polymer interactions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3115-3125, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 447-453 
    ISSN: 0887-6266
    Keywords: polyethylene terephthalate ; low density polyethylene ; isocyanate functional group ; compatibility ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To evaluate the compatibilizing effects of isocyanate (NCO) functional group on the polyethylene terephthalate/low density polyethylene (PET/LDPE) blends, LDPE grafted with 2-hydroxyethyl methacrylate-isophorone diisocyanate (LDPE-g-HI) was prepared and blended with PET. The chemical reaction occurred during the melt blending in the PET/LDPE-g-HI blends was confirmed by the result of IR spectra. In the light of the blend morphology, the dispersions of the PET/LDPE-g-HI blends were very fine over the PET/LDPE blends. DSC thermograms indicated that PET microdispersions produced by the slow cooling of the PET/LDPE-g-HI blends were largely amorphous, with low crystallinity, due to the chemical bonding. The tensile strengths of the PET/LDPE-g-HI blends were higher than those of the PET/LDPE blends having a poor adhesion. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 447-453, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1401-1417 
    ISSN: 0887-6266
    Keywords: polyelectrolytes ; Brownian dynamics ; shear flow ; extensional flow ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational and rheological dynamics of dilute solutions of polyelectrolyte macromolecules undergoing shear and extensional flow are modeled using Nonequilibrium Brownian Dynamics (NEBD) and Configuration-Biased Monte Carlo (CBMC) simulations. The mathematical model utilizes a bead-spring chain with charged beads that interact through a screened Debye-Hückel potential, and that also interact through stretching and bending forces. The diffusion (or Fokker-Planck) equation for the probability density of the positions of the beads of the chain is converted to a Stochastic Differential Equation (SDE), from which the simulation algorithm for the NEBD is obtained. The CBMC is used in the initial chain generation and in determining steady-state properties in elongational flows. Various conformational and rheological quantities, such as the stress and birefringence, are monitored, under both steady-state and transient conditions, with the primary independent variable being the salt concentration (parametrized through the Debye length) and the strength of interaction q, related to the degree of ionization of the chain. It is found that this model is able to describe qualitatively many of the experimentally observed features in such systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1401-1417, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 543-553 
    ISSN: 0887-6266
    Keywords: polyacrylonitrile ; polyimine ; isotacticity ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyacrylonitrile (PAN) films have been “grafted” onto copper electrodes by cathodic polarization and analyzed by infrared spectroscopy and dynamic mechanical thermal analysis (DMTA). The dynamic mechanical response shows two or three transitions depending on the film thickness and the potential deposition. The viscoelastic properties of “ungrafted” PAN films, e.g., solvent cast films of commercially available PAN, are deeply different from those of “electrografted” films. The experimental data support that “ungrafted” chains are paracrystalline in contrast to the “grafted” ones which are essentially amorphous. Moreover, the irreversible transformation of the “grafted” PAN chains observed beyond 225°C is confirmed by Fourier transform infrared (FTIR) analysis and ascribed to an intramolecular cyclization of PAN into polyimine. This reaction occurs rapidly and at a comparatively low temperature with respect to “ungrafted” PAN, which suggests that the “grafted” chain configuration might be predominantly isotactic. The isotacticity and the amorphous structure appear to decrease as the thickness of the PAN film is increased. Literature data and the herein reported observations would suggest a dependence of the amorphous structure of PAN on the chain isotacticity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 543-553, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 583-593 
    ISSN: 0887-6266
    Keywords: enthalpy relaxation ; differential scanning calorimetry ; peak-shift method ; polymethyl(α-n-alkyl)acrylates ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this work, we have investigated by DSC the structural relaxation of amorphous polymethyl(α-n-alkyl)acrylates in which it is possible to change the length of the alkyl chain. We have evaluated the Narayanaswamy parameter, x, which controls the relative contribution of temperature and of structure to the relaxation time, the apparent activation energy, Δh*, and the nonexponentiality parameter, β, of the stretched exponential response function. The results suggest that x increases while Δh* decreases and β remains constant as the length of the side chain increases. This allows us to comment on the effect of chemical modification on the relaxation kinetics. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 583-593, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 641-653 
    ISSN: 0887-6266
    Keywords: impedance spectroscopy ; chemical and physical changes ; glass formers ; reactive polymers ; in situ monitoring ; dielectric properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study was conducted aimed at establishing the nature of chemical and physical phenomena in polymeric and nonpolymeric glass formers that can be observed by impedance measurements. Various systems were investigated that undergo a temporal evolution of structure as a result of chemical reactions and physical processes such as crystallization, vitrification, or phase separation. Distinct and systematic changes in impedance during crystallization and vitrification confirmed that these events could be monitored by impedance spectroscopy. Of particular interest was the potential use of impedance measurements in detecting gelation in crosslinking polymers. It was shown that the experimentally observed “knee” in imaginary impedance during reaction shifts with frequency and, hence, cannot be used to measure gelation. But a new insight at the molecular level was obtained by employing a novel experimental approach based on simultaneous dielectric-infrared measurements. Evidence was generated to support the formation of a hydrogen-bonded complex in the vicinity of gel point in polymer networks, which affords a vehicle for the migration of intrinsic charges and provides a contribution to the overall conductivity. This finding should be explored further because it suggests the possibility of correlating dielectric response with gelation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 641-653, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 665-671 
    ISSN: 0887-6266
    Keywords: clustering ; water ; wood ; adsorption ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Clustering behavior of water molecules during adsorption of water in wood was studied using the Zimm-Lundberg theory. The average cluster size of water molecules was determined with the help of wood adsorption isotherms at five temperatures. The effects of both relative humidity and temperature on average cluster size were studied. Average cluster size progressively increased with an increase in humidity. At humidities corresponding to fiber saturation, larger clusters were formed. Cluster size increased sharply with an increase in temperature at humidities close to saturation. Formation of large clusters at high temperature and humidities close to saturation is attributed to increased fraction of weakly bonded water and capillary condensation in such conditions. A description of adsorption of water in wood was provided in terms of average cluster size. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 665-671, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 705-714 
    ISSN: 0887-6266
    Keywords: molecular weight distribution ; comb copolymer ; branching ; grafting ; nonlinear polymerization ; modeling ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Grafting one type polymer onto a different polymer type may yield a comb-branched copolymer. The branching density has a significant effect on its overall molecular weight distribution. A general model is derived to describe the bivariate distribution of molecular weight and branching density for such comb copolymers. The model is applicable for various grafting mechanisms provided the side chains are randomly grafted onto the backbone. The determining parameters are the molecular weight distributions of backbone and side chains, and the branching density. Analytical expressions are obtained for the cases of the side chains having uniform and Schulz-Zimm distributions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 705-714, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 715-725 
    ISSN: 0887-6266
    Keywords: polyethylene ; ion implantation ; surface structure ; wear ; hardness ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene (PE) film was implanted with 1000-keV Ar+ ions to a fluence of 5 × 1014 ions/cm2 under high vacuum conditions (2.5 × 10-6 torr) and the film surface was investigated by means of microhardness and microwear measurements, and FTIR/ATR, Raman, and XPS techniques. Ion implantation significantly increased the subsurface hardness and also significantly improved the microwear resistance of the polymer. The implanted surface region of the film was found to consist of two distinct layers. One was the outermost carbon layer with a thickness of the order of 10 nm. In this layer, ca. 75% of carbon atoms were combined by graphitic sp2 and diamond-like sp3 bonds, and the remaining 25% had chemical links with oxygen atoms. Spectroscopic data suggested that the sp2-bonded carbons segregated in graphite-like clusters containing imbedded oxygen atoms, interconnected by the sp3-bonded carbons. The other was the subsurface layer resulting from PE oxidation after ion-beam treatment. This layer was characterized by high contents of O—H and C=O groups as well as ester and double bonds. The chemical composition of the layer was uniform and did not vary over the layer thickness of about 1.4 μm. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 715-725, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 783-788 
    ISSN: 0887-6266
    Keywords: poly(ethylene terephthalate) ; sub-Tg ; annealing ; conformation ; infrared spectra ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using FTIR spectroscopy we have examined conformational changes in the quenched and slowly cooled amorphous PET films during physical aging process. It was observed that the amount of trans conformers for quenched sample decreased upon sub-Tg annealing. For the slowly cooled sample that corresponds to a state closer to equilibrium, the amount of trans conformers hardly decreased, but increased gradually during sub-Tg annealing process. The conformational populations of these two samples tend to be identical with annealing time. These results demonstrate that sub-Tg annealing will lead to closer interchain packing and result in the formation of new cohesional entanglements along the chains. In situ FTIR studies on the conformational changes of these samples were also carried out during heating up of the sample through the glass transition region. The results showed that incremental changes of the amount of trans conformers in Samples Q and SC were gradual, while an abrupt change of trans conformers occurred in the sub-Tg annealed samples. These results were in agreement with the formation of the interchain cohesional entanglement due to sub-Tg annealing. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 783-788, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 841-850 
    ISSN: 0887-6266
    Keywords: specific volume ; Tait equation ; compressibility ; scaling parameter ; hole theory ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pressure-volume-temperature (PVT) properties of three commercial samples of poly(dimethylsiloxane) are studied experimentally and theoretically in the temperature range 25-150°C and for pressure to ∼ 3 kbar. The Tait equation is employed to represent the data at elevated pressure. Isothermal compressibilities are computed for the three samples. The melt data are analyzed in terms of the Simha-Somcynsky hole theory, and scaling parameters of pressure, volume, and temperature are obtained. Satisfactory agreement between theory and experiment is found over the entire range of experimental pressures. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 841-850, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 851-859 
    ISSN: 0887-6266
    Keywords: poly(aryl ether ketone)s ; dielectric relaxation spectroscopy ; dynamic mechanical analysis ; α-relaxation ; β-relaxation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation behavior of four amorphous poly(aryl ether ketone)s was investigated using dielectric relaxation spectroscopy and dynamic mechanical analysis. The temperature dependence of the relaxation times of the glass transition process and the cooperative nature of this process were unaffected by changes in polymer structure. The temperature location of the loss peaks for all polymers progressed smoothly between the low frequency of the mechanical measurements and the higher frequencies of the dielectric probe. Differences were observed in mechanical activation energy and dielectric relaxation strength for one polymer which contained a significant concentration of meta linkages, compared with the para-linked polymers, while relaxation broadness was generally greater in the dynamic mechanical mode. Changes in chemical structure had little effect on the shape, intensity, and location of the β-relaxation peak, the main observation being that the Arrhenius activation energy measured by dynamic mechanical analysis was significantly higher than that calculated from the dielectric data. The dielectric β-relaxation was sensitive to absorbed moisture. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 851-859, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1731-1738 
    ISSN: 0887-6266
    Keywords: poly(p-phenylene sulfide) fiber ; zone-drawing ; zone-annealing ; mechanical properties ; DSC thermogram ; viscoelastic properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A zone-drawing and zone-annealing treatment was applied to poly(p-phenylene sulfide) fibers in order to improve their mechanical properties. The zone-drawing (ZD) was carried out at a drawing temperature of 90°C under an applied tension of 5.5 MPa, and the zone-annealing (ZA) was carried out at an annealing temperature of 220°C under 138.0 MPa. The differential scanning calorimetry (DSC) thermogram of the ZD fiber had a broad exothermic transition (Tc = 110°C) attributed to cold-crystallization and a melting endotherm peaking at 286°C. The Tc of the ZD fiber was lower than that (Tc = 128°C) of the undrawn fiber. In the temperature dependence of storage modulus (E′) for the ZD fiber, the E′ values decreased with increasing temperature, but increased slightly in the temperature range of 90-100°C, and decreased again. The slight increase in E′ was attributable to the additional increase in the crosslink density of the network, which was caused by strain-induced crystallization during measurement. The resulting ZA fiber had a draw ratio of 6.0, a degree of crystallinity of 38%, a tensile modulus of 8 GPa, and a tensile strength of 0.7 GPa. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1731-1738, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 937-958 
    ISSN: 0887-6266
    Keywords: thermodynamics ; heteropolymers ; phase diagram ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On the basis of a variational principle a quantitative theory is developed enabling a thermodynamic description in terms of mean field approximation of heteropolymer mixtures of macromolecules with an arbitrary distribution for both degree of polymerization and composition. Rather simple general equations are derived to calculate compositions and volume fractions of spatially homogeneous macroscopic phases as well as to find the cloud-point curve, spinodal, and critical points. Potentialities of general theory are illustrated for copolymers synthesized by traditional methods. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 937-958, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 983-989 
    ISSN: 0887-6266
    Keywords: positron annihilation ; free-volume ; Nafion ; free-volume size distribution ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report a new result of free-volume hole size distribution in water and ethanol-swollen Nafion-117 polymer. With the increase in water content, free-volume hole size decreases, but overall the volume fraction increases. The hole size distribution in dry polymer is seen to be distinctly different from hydrated membranes. The narrow and symmetric distribution in hydrated membrane as compared to dry membrane is believed to be a consequence of crosslinking due to cluster formation. In alcohol-swollen membranes, on the other hand, not only are the free-volume size and fraction seen to be higher, the hole size distribution is seen to be broader compared to dry or hydrated membranes, indicating the effect of penetration of alcohol into the hydrophobic backbone region. We have also examined our results vis-a-vis reported gas diffusion studies in Nafion in the framework of existing free-volume model. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 983-989, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1013-1024 
    ISSN: 0887-6266
    Keywords: nonlinear optical polymer ; pressure ; chromophore reorientation ; poly(alkyl methacrylates) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Activation volumes for chromophore reorientation were measured for a series of guest-host polymeric materials, indicating a significant coupling between chromophore motion and the glassy α and β relaxation dynamics of the polymer host. The specific systems studied were formed by individually dissolving N,N-dimethyl-p-nitroaniline (DpNA), 4-(dimethylamino)-4′-nitrotolane (DMANT), 4-(diethylamino)-4′-nitrotolane (DEANT), and 1-((4-(dimethylamino)phenyl)ethynyl)-4-((4-nitrophenyl)ethynyl)benzene (DMAPEANT) in poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and poly(isobutyl methacrylate) (PiBMA). In each of these systems, the isothermal, sub-Tg decay of the second-order optical susceptibility χ(2) was monitored as a function of pressure using second harmonic generation. In each system, the observed decay of χ(2) was represented by a stretched exponential equation from which the decay time τ0 and decay distribution width βKWW were determined. For each dopant molecule, the decrease in activation volume with the increasing size of the polymer host's alkyl side group and the pressure dependence of βKWW were indicative of partial coupling between chromophore rotation and the glassy β relaxation dynamics of the polymer host. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1013-1024, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1091-1094 
    ISSN: 0887-6266
    Keywords: electrorheological fluids (ERFs) ; poly(dimethyl siloxane) gels ; artificial muscle ; electromechanical actuators ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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  • 75
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1115-1128 
    ISSN: 0887-6266
    Keywords: interface structure ; fluorescence energy transfer ; polymer blends ; latex films ; poly(methyl methacrylate) ; poly(butyl methacrylate-co-butyl acrylate) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Immiscible polymer blend films were formed by air drying aqueous dispersions containing mixtures of a high-Tg latex, poly(methyl methacrylate), and a film-forming low-Tg latex, poly(butyl methacrylate-co-butyl acrylate). Fluorescence energy transfer experiments were used to characterize the interfaces in these films, in which one component was labeled with a donor dye and the other with an acceptor. The quantum efficiency of energy transfer (ΦET) between the donors and acceptors is influenced by the interfacial contact area between the two polymer phases. As the amount of soft component in the blend is increased, ΦET approaches an asymptotic value, consistent with complete coverage of the hard polymer surface with soft polymer. This limiting extent of energy transfer is very sensitive to the total surface area in the film, with correspondingly more energy transfer at constant volume fraction for small hard particles. Some of the details of the energy transfer are revealed through a fluorescence lifetime distribution analysis. The presence of ionic surfactant (sodium dodecyl sulfate) in the dispersion from which the latex blend film is prepared reduces the cross-boundary energy transfer by 30%, which implies that in these films the surfactant decreases the interfacial contact. After annealing the surfactant-free blends above 100°C, we observe an increase in energy transfer, consistent with a broader interface between the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1115-1128, 1998
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  • 76
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1153-1165 
    ISSN: 0887-6266
    Keywords: even-odd nylons ; lamellar crystals ; structure ; hydrogen-bonding schemes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 6 9 has been shown to have structures with interchain hydrogen bonds in both two and in three directions. Chain-folded lamellar crystals were studied using transmission electron microscopy and sedimented crystal mats and uniaxially oriented fibers studied by X-ray diffraction. The principal room-temperature structure shows the two characteristic (interchain) diffraction signals at spacings of 0.43 and 0.38 nm, typical of α-phase nylons; however, nylon 6 9 is unable to form the α-phase hydrogen-bonded sheets without serious distortion of the all-trans polymeric backbone. Our structure has c and c* noncoincident and two directions of hydrogen bonding. Optimum hydrogen bonding can only occur if consecutive pairs of amide units alternate between two crystallographic planes. The salient features of our model offer a possible universal solution for the crystalline state of all odd-even nylons. The nylon 6 9 room-temperature structure has a C-centered monoclinic unit cell (β = 108°) with the hydrogen bonds along the C-face diagonals; this structure bears a similarity to that recently proposed for nylons 6 5 and X3. On heating nylon 6 9 lamellar crystals and fibers, the two characteristic diffraction signals converge and meet at 0.42 nm at the Brill temperature, TB · TB for nylon 6 9 lamellar crystals is slightly below the melting point (Tm), whereas TB for nylon 6 9 fibers is ≅ 100°C below Tm. Above TB, nylon 6 9 has a hexagonal unit cell; the alkane segments exist in a mobile phase and equivalent hydrogen bonds populate the three principal (hexagonal) directions. A structure with perturbed hexagonal symmetry, which bears a resemblance to the reported γ-phase for nylons, can be obtained by quenching from the crystalline growth phase (above TB) to room temperature. We propose that this structure is a “quenched-in” perturbed form of the nylon 6 9 high-temperature hexagonal phase and has interchain hydrogen bonds in all three principal crystallographic directions. In this respect it differs importantly from the γ-phase models. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1153-1165, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1557-1566 
    ISSN: 0887-6266
    Keywords: polyesters ; PET ; PEN ; PEI ; 13C NMR ; dynamics ; nuclear relaxation times ; gas diffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamics of amorphous aromatic polyesters consisting of poly(ethylene terephthalate) (PET), poly(ethylene isophthalate) (PEI), and poly(ethylene 2,6-naphthalenedicarboxylate) (PEN) has been investigated by means of solid state CPMAS 13C NMR. Proton T2, 13C T1ρ, and proton T1ρ decays have been measured in particular, and the experimental data fitted to suitable model functions to determine best relaxation parameters. The fitting results show for proton T2 and 13C T1ρ measurements the presence of two components with different relaxation times and intensities, arising from different motional domains. The proton T1ρ, on the contrary, shows a single component which limits the dimensions of the two regions to less than 20 Angstroms. The dependence of 13C T1ρ values on two different irradiating field strengths (H1 = 38 KHz, H1 = 60 KHz) allowed the assignment of each component to relatively rigid and mobile regions. By comparing the three polymers we observe that PEN and PEI have a similar relaxation behavior, while a higher fraction of mobile components was found for PET. These differences are believed to arise mainly from local motions of the aromatic rings. The relaxation measurements have been evaluated to suggest a correspondence to O2 and CO2 gas permeabilities in PET, PEI, and PEN. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1557-1566, 1998
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  • 78
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2165-2175 
    ISSN: 0887-6266
    Keywords: temperature-modulated differential scanning calorimetry ; DSC ; heat capacity ; glass transition ; thermal relaxation ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transition can be measured at different experimental conditions. Using spectroscopic methods at relative high frequency the α-relaxation is measured in the thermodynamic equilibrium. In the caloric case we call this phenomenon thermal relaxation transition (TRT). With a conventional differential scanning calorimeter (DSC) the transition of the equilibrium (the melt) into a nonequilibrium (the glassy state) is measured. This effect is called thermal glass transition (TGT). In contrast to the TGT, the TRT can be described using the linear response approach. The temperature-modulated differential scanning calorimetry (TMDSC) technique superimposes a periodical temperature perturbation upon the constant scanning rate of conventional DSC. This technique combines a spectroscopic method with a linear temperature scan. Both the TGT and the TRT are measured simultaneous. Because the frequencies are relatively low in a TMDSC experiment, the temperature ranges of both transitions overlap. In this case, the experimental results show an influence of the TGT on the TRT. The reason of that is the deviation from the nonequilibrium. In this case, the fictive temperature is different from the external temperature. This effect can be described by means of a Tool-Narayanaswamy-Moynihan model for the TGT. Based on this model, a description of the complex heat capacity close to the thermal glass transition is shown. The influence of the beginning freezing-in process on the thermal relaxation is characterized by the fictive temperature. Using the presented description, a quantitative calculation of the nonlinear effects in the thermal relaxation is possible. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2165-2175, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2177-2189 
    ISSN: 0887-6266
    Keywords: yield ; polyethylene ; stem length ; crystal plasticity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The yield stress behavior of a range of polyethylene materials which differ with respect to their short chain branch content has been studied. Measurements carried out over a wide range of temperatures have shown that there is a sudden transition in the behavior of the yield stress at a temperature which is dependent on both the grade of material and the applied strain rate. These results are in agreement with previous results found from analysis of the yield strain behavior.Above the transition temperature the materials all behave in a nonlinear viscoelastic manner, and the yield process is considered as being propagation controlled. Below the transition temperature the materials all behave in an elastic-plastic manner, and the yield process is considered as being nucleation controlled. Below the transition temperature the temperature dependence of the yield stress is determined by the thickness of the crystalline lamellae. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2177-2189, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2225-2235 
    ISSN: 0887-6266
    Keywords: PEEK ; composite ; stability ; nonisothermal ; crystallinity ; melting ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal stability of a short carbon-fiber-reinforced PEEK composite was assessed by thermogravimetry and by a Rheometrics dynamic analyzer. The results indicated that holding for 10 min at 380°C was a suitable melting condition to avoid the thermooxidative degradation under air. After proving that the heating rate of 50°C/min can be used to evaluate the crystallinity, a heating stage was used to prepare nonisothermally crystallized specimens using cooling rates from 1 to 100°C/min after melting at 400°C for 3 or 15 min. The degree of crystallinity and the melting behavior of these specimens were investigated by DSC at a heating rate of 50°C/min. The presence of three or four regions indicated that the upper melting temperature, Tm, changed with the crystallization temperature. The first region with the highest Tm, which corresponded to the cooling rate of 1°C/min, can be associated with the crystallization in regime II. There was a second region where Tm decreased as the amount of crystals formed in regime II decreased with increasing cooling rate from 5 to 20°C/min. The third region, a plateau region, corresponded to regime III condition in which the crystals were imperfect. In the fourth region, the cooling was so fast that crystallization was incomplete during the cooling for the melting condition of 400°C for 15 min. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2225-2235, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2513-2523 
    ISSN: 0887-6266
    Keywords: block copolymer ; thermoplastic elastomer ; physical gel ; order-disorder transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoplastic elastomer gels (TPEGs) composed of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and a low-volatility, midblock-compatible mineral oil have been investigated here to ascertain the effects of composition on TPEG morphology, and temperature on mechanical properties. Cryofracture-replication transmission electron micrographs reveal the existence of spheroidal bumps due to copolymer micelles, as well as a network of irregularly shaped, high-aspect-ratio features. Since the density of this network decreases with increasing oil concentration, these features are attributed to copolymer grain boundaries. Micellar periodicities are discerned from small-angle X-ray scattering as a function of copolymer concentration and compared with previously reported data from related systems. Dynamic rheological tests performed up to 140°C indicate that the linear viscoelastic regime for these TPEGs decreases with both increasing copolymer concentration and temperature. A concentration-dependent thermal transition, signified by an abrupt reduction in the dynamic elastic modulus (G′), has also been identified.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2513-2523, 1998
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  • 82
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2949-2959 
    ISSN: 0887-6266
    Keywords: ultrasound ; crystallization kinetics ; film formation ; polychloroprene ; shear modulus ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report the application of an ultrasonic shear wave reflection technique for the investigation of film formation and crystallization kinetics of one amorphous and two semicrystalline polychloroprene samples with different gel content. Both isothermal and temperature-dependent measurements of the complex dynamic shear modulus (G* = G′ + iG″) have been performed at a frequency of 5.32 MHz. The process of film formation during the evaporation of water is expressed by a stepwise increase of the shear modulus. For the semicrystalline samples a further increase, which is due to crystallization, can be observed. Film formation and crystallization are delayed for the sample with high gel content and its minor final modulus is explained by a lower degree of crystallinity. The time-dependent increase of the shear modulus due to the growth of spherulites has been analyzed by the Avrami equation combined with the Kerner model for the modulus of a two-phase composite (spherulites in an amorphous matrix). The dynamic shear modulus for the spherulites has been estimated by a model introduced by Halpin and Kardos. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2949-2959, 1998
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  • 83
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2981-3000 
    ISSN: 0887-6266
    Keywords: sorption ; diffusion ; acetone ; poly(ethylene terephthalate) ; poly(ethylene 2,6-naphthalate) ; copolymers ; positron annihilation lifetime spectroscopy ; infrared spectroscopy ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Random copolymers of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalate) (PEN) were synthesized by melt condensation. In a series of thin, solvent cast films of varying PEN content, acetone diffusivity and solubility were determined at 35°C and an acetone pressure of 5.4 cm Hg. The kinetics of acetone sorption in the copolymer films are well described by a Fickian model. Both solubility and diffusivity decrease with increasing PEN content. The acetone diffusion coefficient decreases 93% from PET to PET/85PEN, a copolymer in which 85 weight percent of the dimethyl terephthalate in PET has been replace by dimethyl naphthalate 2,6-dicarboxylate. The acetone solubility coefficient in the amorphous regions of the polymer decreases by approximately a factor of two over the same composition range. The glass/rubber transition temperatures of these materials rise monotonically with increasing PEN content. Copolymers containing 20 to 80 wt % PEN are amorphous. Samples with 〈20% or 〉80% PEN contain measurable levels of crystallinity. Estimated fractional free volume in the amorphous regions of these samples is lower in the copolymers than in either of the homopolymers. Relative free volume as probed by positron annihilation lifetime spectroscopy (PALS) decreases systematically with increasing PEN content. Acetone diffusion coefficients correlate well with PALS results. Infrared spectroscopy suggests an increase in the fraction of ethylene glycol units in the trans conformation in the amorphous phase as the concentration of PEN in the copolymer increases. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2981-3000, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3035-3048 
    ISSN: 0887-6266
    Keywords: epoxy ; absorption ; water ; positron annihilation lifetime spectroscopy ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Epoxy resins absorb significant quantities of moisture, typically 1 to 7% by weight for various formulations, which can greatly compromise their physical properties. It is known that polarity of the epoxy is a significant factor in determining the ultimate moisture uptake. However, the contribution from molecular topology still remains vague. In this work, the effects of molecular topology are elucidated by synthesizing novel epoxies where the polarity is maintained constant but the topology is systematically altered. The molecular topology is quantified in part via Positron Annihilation Lifetime Spectroscopy (PALS) in terms of the nanometer-sized voids, or nanovoids, that are also commensurate with typical interchain distances. The nanovoids are separated into their absolute zero and thermally fluctuating fractions by performing PALS measurements over a wide range of temperatures. A strong correlation is observed between the absolute zero hole volume fraction and the ultimate moisture uptake. Although the correlation is clear, the absolute zero hole volume fraction alone is not sufficient to predict the ultimate moisture uptake, and network polarity must also be considered. It is surmised that the role of the nanovoids is to open the epoxy matrix and alleviate steric hindrances that may prevent a water molecule from associating with a polar group. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3035-3048, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3079-3086 
    ISSN: 0887-6266
    Keywords: diffusion ; block copolymer ; monomeric friction factor ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Monomeric friction factors, Ξ, for polystyrene (PS), polyisoprene (PI), and a polystyrene-polyisoprene (SI) diblock copolymer have been determined as a function of temperature in four poly(styrene-b-isoprene-b-styrene-b-isoprene) tetrablock copolymer matrices. The Rouse model has been used to calculate the friction factors from tracer diffusion coefficients measured by forced Rayleigh scattering. Within the experimental temperature range the tetrablock copolymers are disordered, allowing for measurement of the diffusion coefficient in matrices with average compositions determined by the tetrablock copolymers (23, 42, 60, and 80% styrene by volume). Remarkably, for a given matrix composition the styrene and isoprene friction factors are essentially equivalent. Furthermore, at a constant interval from the system glass transition temperature, Tg, all of the friction factors (obtained from homopolymer, diblock copolymer, and tetrablock copolymer dynamics) agree to within an order of magnitude. This is in marked contrast to results for miscible polymer blends, where the individual components generally have distinct composition dependences and magnitudes at constant T - Tg. The homopolymer friction factors in the tetrablock matrices were systematically slightly higher than those of the diblock, which in turn were slightly higher than those of the homopolymers in their respective melts, when all compared at constant T - Tg. This is attributed to the local spatial distribution of styrene and isoprene segments in the tetrablocks, which presents a nonuniform free energy surface to the tracer molecules. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3079-3086, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3087-3100 
    ISSN: 0887-6266
    Keywords: polymer dynamics ; light scattering spectroscopy ; probe diffusion ; coupling model ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We studied translational diffusion of dilute monodisperse spheres (diameters 14 〈 d 〈 455 nm) in aqueous 1 MDa hydroxypropylcellulose (0 ≤ c ≤ 7 g/L) at 25°C using quasielastic light scattering. Spectra are highly bimodal. The two spectral modes (“slow,” “fast”) have different physical properties. Probe behavior differs between small (d 〈 Rh) and large (d ≥ Rg) probes; Rh and Rg are the matrix polymer hydrodynamic radius and the radius of gyration, respectively. We examined the dependences of spectral lineshape parameters on d, c, scattering vector q, and viscosity η for all four probe-size and mode-type combinations. We find three time scale-separated modes: (1) a large-probe slow mode has properties characteristic of particle motion in a viscous medium; (2) a large-probe fast mode and small-probe slow modes share the same time scale, and have properties characteristic of probe motion coupled to internal chain dynamics; and (3) a small-probe fast mode has properties that can be attributed to the probe sampling local chain relaxations. In the analysis, we also attempted to apply the coupling/scaling (CS) model of Ngai and Phillies [Ngai, K. L., Phillies, G. D. J. J. Chem. Phys., 105, 8385 (1996)] to analyze our data. We find that the second mode is described by the coupling/scaling model for probe diffusion; the first and third modes do not follow the predictions of this model. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3087-3100, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3137-3145 
    ISSN: 0887-6266
    Keywords: X-ray analysis ; copoly(ester-imide) ; thermotropic liquid crystalline polymers ; random copolymers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of a thermotropic liquid crystalline copoly(ester-imide) prepared from p-hydroxybenzoic acid (48 mol %), 4,4′-dihydroxybenzophenone (26 mol %), and N,N′-bis(trimellitimide)hexane (26 mol %) has been investigated by X-ray diffraction. X-ray fiber diagrams of as-spun and annealed fibers contain a series of aperiodic layer lines reminiscent of those seen for fibers of other copolymers that have extended chain conformations and completely random monomer sequences. The positions of these layer lines were reproduced approximately in simulation of the X-ray scattering by a fully extended chain of completely random sequence, and the match was improved to within experimental error when we considered a stereochemically acceptable sinuous chain. This agreement was lost when the sequence statistics deviated were completely random. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3137-3145, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2339-2348 
    ISSN: 0887-6266
    Keywords: epoxy ; curing ; generating function ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The systems of diepoxides cured with primary amine in presence of an monoepoxide, monofunctional reactive, under equal stoichiometric ratio has been analyzed by a generating function method. The average degree of polymerization, which changed with time or conversion, and gel point were calculated. The profiles of the degree of polymerization and critical conversion are dependent on the content of and relative reactivities of epoxy groups. For a system with the same ratio, the critical epoxy conversion increases with increasing reactivity. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2339-2348, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2371-2378 
    ISSN: 0887-6266
    Keywords: liquid crystalline ; polymers ; X-ray diffraction ; fibers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis and a partial characterization of segmented liquid crystalline polymers with 3,3′-diallyl-4,4′-dihydroxybiphenyl unit in the rigid moiety is reported. The general formula of polymers is [-p-C6H4-COO-p-C6H3(R)-p-C6H3(R)-OOC-p-C6H4-O-(CH2)nO-]x, with n = 6, 8, 10, 12, and R = —CH2—CH=CH2. All polymers have nematic liquid-crystalline behavior. At room temperature, annealed fiber samples of polymers show a complex polymorphism. Three phases have been isolated with very large unit cells accommodating 6 or 12 chains. The projection of the molecular packing in a plane perpendicular to the c axis is characterized by the organization of chains in a two-dimensional hexagonal or quasi-hexagonal array. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2371-2378, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2413-2421 
    ISSN: 0887-6266
    Keywords: positron annihilation ; polyimide ; ion implantation ; membrane ; permeability ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 6FDA-pMDA polyimide membranes were implanted with 140 keV N+ ions to fluences between 2 × 1014 and 5 × 1015 cm-2. Variable energy positron annihilation spectra were taken and spectral features compared to previously reported changes in gas permeability and permselectivity of these membranes as a function of ion fluence. Positron data corroborate the explanation of these changes in terms of molecular damage caused by the implant: for fluences up to about 1 × 1015 cm-2, the concentration of irradiation-induced defects merely increases with implant fluence; while fluences exceeding this threshold value create a second type of positron annihilation site, thereby marking a distinct change in the structure of the polymer, which is responsible for the vast improvement of gas permselectivity data found at the same threshold fluence. PACS codes: 78.70.Bj - positron annihilation; 61.82.Pv - polymers, organic compounds; 61.72.Ww - doping and impurity implantation. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2413-2421, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3127-3136 
    ISSN: 0887-6266
    Keywords: block copolymers ; thin films ; patterned surfaces ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We present results from a numerical study of a coarse-grained model of diblock copolymer (BCP) thin films cast on a chemically patterned surface. The patterned surface contains chemical inhomogeneities with a repeat spacing length scale comparable to the linear size of the BCP molecules. We find that the orientation of the lamellae in the thin film and the overlap of the film morphology with the preassigned surface pattern is strongly influenced by the commensurability between the bulk unconstrained lamellar size λ*, and the linear size of the surface inhomogeneities w. PACS Numbers: 64.60.Cn, 61.41.+e, 64.60.My, 64.75.+g. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3127-3136, 1998
    Additional Material: 12 Ill.
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  • 92
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2677-2681 
    ISSN: 0887-6266
    Keywords: sulfonated SEBS ; viscosity property ; molecular aggregation ; freezing-thawing treatment ; shear-thickening ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dilute solution properties of lightly sulfonated hydrogenated styrene-butadiene-styrene block copolymer (S-SEBS) dissolved in tetrahydrofunan (THF) were studied by viscometry. The ring conformation in dilute regime can be deduced from the intrinsic viscosity data. It is believed that this special conformation results from the location of ionic group at both two-end blocks. The intermolecular aggregation can be observed when the solutions undergo the freezing-thawing process in the same concentration region. The extent of aggregation is affected by the freezing-thawing cycle times, water content in THF, and the counterion radii, etc. The properties of the aggregation equilibrium are also discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2677-2681, 1998
    Additional Material: 6 Ill.
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  • 93
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2703-2716 
    ISSN: 0887-6266
    Keywords: calorimetry ; dielectrics ; diffusion ; monoamine-triepoxide ; thermoset ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Calorimetry and dielectric relaxation spectroscopy during the growth of a polymer network in the stoichiometric mixture of a triepoxide with 4-chloroaniline have been performed in separate experiments to investigate the increase in the relaxation time with the number of covalent bonds. A comparison with the corresponding study of triepoxide-aniline and triepoxide-3-chloroaniline mixtures shows that steric hindrance of the amine group by chlorine slows the molecular dynamics and the relaxation time of the state containing a fixed number of bonds. The polymerization kinetics measured during ramp heating does not yield a reliable activation energy. A recent empirical relation between the relaxation time and the extent of polymerization, and the condition for the onset of diffusion-control kinetics have been examined using the data for these three polymerizing mixtures. The results show substantial deviations from the empirical relation and appear to conflict with our basic understanding of the polymerization process. It is shown mathematically that features attributed to the onset of diffusion-controlled kinetics can arise from thermochemical behavior alone, without reference to the molecular dynamics. An earlier theory for the change in the kinetics of an addition reaction from mass control to diffusion control has been considered, and is seen as relevant to the polymerization reactions. It is argued that the dielectric relaxation rate does not directly indicate the chemical reaction rate because the reorientational motion of the dipolar entities may not be coupled to the rotational and translational diffusion that brings the sterically hindered chemically reacting sites together. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2703-2716, 1998
    Additional Material: 7 Ill.
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  • 94
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1-9 
    ISSN: 0887-6266
    Keywords: small-angle neutron scattering ; SANS ; polystyrene ; polyvinylmethylether ; radius of gyration ; Zimm analysis ; random phase approximation ; phase diagram ; polymer blends ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle neutron scattering was used to measure the radius of gyration and thermodynamics of blends of poly(vinylmethylether) (PVME) at dilute concentration in deuterated polystyrene (PSD). The data were analyzed using the Zimm equation and the random phase approximation theory. For PVME with a weight-average molecular weight of 38,400 the value of the radius of gyration, Rg, was found to be 47 Å in the limit of the concentration of PVME extrapolated to zero. Analysis of the temperature dependence of the Flory interaction parameter, χ/v0, indicates that phase separation should occur at approximately 300°C for a sample with φPVME ≅ 9%. No significant temperature dependence of Rg was found over the experimental range studied. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1-9, 1998
    Additional Material: 5 Ill.
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  • 95
    ISSN: 0887-6266
    Keywords: liquid crystal ; block copolymer ; polyester block ; polymethacrylate block ; magnetic field ; X-ray diffraction ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase and orientational behaviors of a series of liquid crystalline (LC) AB-type diblock copolymers comprising thermotropic main-chain (MC) polyester and side-group (SG) polymethacrylate blocks were investigated by X-ray diffraction. The MC and SG blocks were phase separated and gave rise to their individual mesophases that coexisted at equilibrium. The samples were oriented by using either a magnetic field or a mechanical field. In magnetically aligned samples both the MC and SG microphases were oriented with their smectic planes orthogonal to the magnetic field direction, independent of the copolymer composition. Mechanically aligned, fiber samples showed different orientations of the MC and SG smectic planes for different sample compositions. In this case the disposition of the smectic planes of the MC and SG blocks was driven by the relative length of the two blocks. Some features of the X-ray patterns of the copolymers were compared to those of the MC and SG homopolymers. In addition, the MC smectic domains crystallized on annealing without affecting the orientation that had been achieved by applying a magnetic field. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 21-29, 1998
    Additional Material: 11 Ill.
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  • 96
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 49-54 
    ISSN: 0887-6266
    Keywords: substituted poly(paraphenylene) ; phase transitions ; synchrotron radiation ; mesophases ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal behavior of poly(para-2,5-didecyl-p-phenylene) has been investigated by differential scanning calorimetry and real time X-ray diffraction. Poly(para-2,5-didecyl-p-phenylene) is a semicrystalline material that crystallizes in a layered structure. The system exhibits two thermal transitions in the investigated temperature range. The first one, occurring at lower temperatures, provokes a reduction of the layered spacing accompanied by an appreciable disordering of the lateral side chains. Above the first transition the material is shearable, highly viscous, and birefringent. Thus, we have associated this transition to the formation of a layered mesophase. The higher temperature transition exhibits a twofold endothermic DSC peak and is characterized by the disappearance of X-ray diffracted intensity. At temperatures above the second transition the system presents the characteristics of an isotropic melt. Consequently, we have associated this transition with the complete disordering of the polymeric backbones. By following an appropriate thermal treatment it has been shown that the twofold shape of the endotherm characterizing the higher temperature transition can be changed into a single endotherm. This effect has been interpreted as being due to the kinetics of main-chain ordering. This ordering seems to proceed by the initial growth of domains with a high level of order followed by the subsequent increase of these domains through the inclusion of less ordered material. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 49-54, 1998
    Additional Material: 8 Ill.
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  • 97
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 85-93 
    ISSN: 0887-6266
    Keywords: polybutadiene ; poly(methyl methacrylate) ; poly(butadiene-block-methyl methacrylate) ; compatibilization ; micelle ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Compatibilization of blends of polybutadiene and poly(methyl methacrylate) with butadiene-methyl methacrylate diblock copolymers has been investigated by transmission electron microscopy. When the diblock copolymers are added to the blends, the size of PB particles decreases and their size distribution gets narrower. In PB/PMMA7.6K blends with P(B-b-MMA)25.2K as a compatibilizer, most of micelles exist in the PMMA phase. However, using P(B-b-MMA)38K as a compatibilizer, the micellar aggregation exists in PB particles besides that existing in the PMMA phase. The core of a micelle in the PMMA phase is about 10 nm. In this article the influences of temperature and homo-PMMA molecular weight on compatibilization were also examined. At a high temperature PB particles in blends tend to agglomerate into bigger particles. When the molecular weight of PMMA is close to that of the corresponding block of the copolymer, the best compatibilization result would be achieved. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 85-93, 1998
    Additional Material: 8 Ill.
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  • 98
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 113-126 
    ISSN: 0887-6266
    Keywords: enthalpy relaxation ; physical aging ; DSC ; glassy state ; thermoplastic polymers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enthalpy relaxation of a series of linear amorphous polyesters (poly(propylene isophthalate) (PPIP), poly(propylene terephthalate) (PPTP), poly(ethylene terephthalate) (PETP), and poly(dipropylene terephthalate) (PDPT)) has been investigated by differential scanning calorimetry (DSC). These polyesters have been annealed at equal undercooling below their respective glass transition temperatures, Tg, (Tg - 27°C, Tg - 15°C, and Tg - 9°C) for periods of time from 15 min to 480 h. The key parameters of structural relaxation, namely the apparent activation energy (Δh*), the nonlinearity parameter (x) and the nonexponentiality parameter (β), have been determined for each polyester and related to an effective relaxation rate (1/τeff) and to the chemical structure. We observe that the variation of the structural relaxation parameters shows a trend that is common to other polymeric systems, whereby an increase of x and β corresponds a decrease in Δh*. The comparison of these parameters in PETP and in PPTP gives information about the effect of the introduction of a methyl group pendant from the main chain; the x parameter increases (i.e., a reduced contribution of the structure to the relaxation times), β increases (i.e., a narrow distribution of relaxation times), and Δh* decreases. Additionally, enthalpy relaxation experiments show that a decrease of Δh* correlates with an increase of 1/τeff, when they are measured at a fixed value of the excess enthalpy, δH. The introduction of an isopropyl ether group in PDPT with respect to PPTP decreases both x and β, but increases Δh*, which the rate of relaxation decreases. The ring substitution in PPTP and PPIP originates less significant changes in the structural parameters. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 113-126, 1998
    Additional Material: 8 Ill.
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  • 99
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 163-169 
    ISSN: 0887-6266
    Keywords: acetone ; poly(ethylene terephthalate) ; mass transport ; solvent-induced crystallites ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The acetone transport in poly(ethylene terephthalate) (PET) and related phenomena was investigated. Based on Harmon's model for Case I, Case II, and the anomalous transport, we analyzed the data of mass uptake. The diffusivity for Case I and the velocity for Case II satisfied the Arrhenius plot. It was found that the solvent moves from outer surfaces to the center according to Case I kinetics, and there is movement in the opposite direction according to Case II kinetics during the mass uptake. This result indicated that pure Case II behavior did not appear in the PET-acetone system. The saturated amount of acetone in PET satisfied the van't Hoff plot. X-ray diffraction pattern and DSC curve showed solvent-induced crystallites and thermal crystallites. The results of density measurement explained the difference of the sorption kinetics between the acetone-treated PET crystallites and thermally treated PET. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 163-169, 1998
    Additional Material: 5 Ill.
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  • 100
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 617-627 
    ISSN: 0887-6266
    Keywords: isotactic polypropylene foams ; supercritical propane solutions ; high surface areas ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization of isotactic polypropylene (iPP) from homogeneous solution in supercritical propane yields open-cell foams of high surface area (120-150 m2/g). Their morphology usually consists of microspheres with a dense core and a porous periphery of radiating fibrils. Pore radii covering the mesopore range (2-50 nm), making their largest contribution at 10-20 nm, were calculated from nitrogen adsorption isotherms. Surface areas of the correct order of magnitude are obtained by assuming that gas adsorption takes place on the surfaces of lamellar crystals. Crystallization of iPP from n-butane and n-heptane generates foams of lower mesoporosity and smaller surface area. These more “liquid-like” solvents do not allow the formation of an open network of mesopores or they promote its collapse upon their removal. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 617-627, 1998
    Additional Material: 13 Ill.
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