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  • 1975-1979  (2,674)
  • 1965-1969  (1,904)
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  • Physics  (4,390)
  • Cat
  • 1
    ISSN: 1435-1463
    Keywords: Cat ; electrical stimulation ; serotonin ; splanchnic nerves ; substance P
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The blood levels of serotonin (5-HT) and substance P (SP) in the portal vein were studied after splanchnic nerve stimulation in the cat. The portal levels of both substances were studied before, during and after splanchnic nerve stimulation. There was a twofold increase in 5-HT during stimulation whilst the SP concentration remained unchanged. These results suggest that the nervous control of the amine release into the portal stream and the mechanism that regulates the release of the polypeptide is not the same.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 34 (1979), S. 273-286 
    ISSN: 1432-1106
    Keywords: Stimulus velocity ; Single cell responses ; LGN ; Area 17 ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neuronal responses to moving visual stimuli were recorded in the lateral geniculate nucleus (LGN) and area 17 of cats. Response duration (DE), number of spikes (NT), and mean frequency (FM) were estimated from the response histograms and analysed for their dependence on stimulus velocity. In the LGN, for about 2/3 of cells these response parameters changed monotonically with velocity up to about 100 °/s. In 1/3 of the cells, the response frequency was tuned to velocity. The speed at which individual cells reached a peak or plateau firing rate was correlated with their receptive field size. In area 17, most neurones were tuned to velocity. Nine out of 59 cells were insensitive to stimulus speed in that they responded equally well at stimulus velocities up to about 10 °/s. The results suggest that at higher levels in the nervous system information about velocity is represented in discrete groups of neurones. It is pointed out that different response parameters may be relevant for different perceptual phenomena associated with movement. The significance of integrational properties and lateral inhibition of nerve cells for the development of complex response properties is discussed.
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  • 3
    ISSN: 1432-1106
    Keywords: Thermoreceptors ; Gastro-intestinal tract ; Vagal nerve ; C Fibres ; Cat ; Thermorecepteurs ; Tractus gastro ; Intestinal ; Nerf vague ; Fibres amyéliniques ; Chat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Chez des chats anesthésiés, des décharges sensitives vagales ont été enregistrées dans le ganglion plexiforme à l'aide d'électrodes extracellulaires en verre. Nous avons trouvé au niveau de l'antre et du duodénum, des récepteurs toniques, activés par des solutions chaudes (38–51 ° C avec un optimum à 46–49 ° C) ou froides (36–10 ° C avec un optimum à 12–10 ° C). Ces récepteurs ne répondent ni aux stimulus mécaniques (compression et distension des viscères), ni aux stimulus chimiques (perfusion avec des solutions glucosées ou acides). Ces récepteurs n'appartiennent donc pas au groupe des récepteurs polymodaux, mais ils doivent être considérés comme de véritables thermorécepteurs spécifiquement sensibles au chaud ou au froid. Les thermorécepteurs de la région gastro-duodénale sont connectés à des fibres vagales amyéliniques (vitesse de conduction: 0,8–1,4 m/s). Par ailleurs, le rôle éventuel des thermorécepteurs vagaux de la région gastro-duodénale dans la régulation de la motilité digestive a été recherché. En dérivant simultanément l'EMG en plusieurs points du tractus gastro-duodénal, il a été possible de démontrer que les stimulations froides et chaudes du duodénum, qui mettent en jeu les thermorécepteurs, provoquent une inhibition de l'activité électrique de l'antre. Les modifications persistent apèrs bisplanchnectomie, mais disparaissent complètement après bivagotomie. A partir de ces faits, nous en avons conclu que les thermorécepteurs vagaux sont impliqués dans la régulation nerveuse de la motilité gastro-duodénale.
    Notes: Summary In anaesthetized cats, sensory vagal units were recorded in the nodose ganglion by means of extracellular glass microelectrodes. In the antrum and the duodenum we have found receptors tonically activated by warm (38–51 ° C with an optimum at 46–49 ° C) or cold (36–10 ° C with an optimum at 12–10 ° C) solutions. These receptors did not respond to mechanical stimuli (compression and distension of the viscera) and to chemical ones (perfusion with glucose and acid solutions). Thus they did not belong to polymodal type, but they must be considered as true thermoreceptors, specifically sensitive to warm or cold stimulations. The gastro-duodenal thermoreceptors were connected to non-medullated vagal fibres (conduction velocity: 0.8–1.4 m/s). On the other hand, the role of the gastro-duodenal vagal thermoreceptors in the regulation of the digestive motility was studied. By using several electromyographic recordings, it was possible to show that the cold and warm stimulations of the duodenum which elicited thermoreceptor responses, induced an inhibition of the electrical activity of the antrum. The changes persisted after bisplanchnectomy, but disappeared completely after bivagotomy. From these facts it was concluded that the vagal thermoreceptors were involved in the nervous regulations of the gastro-duodenal motility.
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  • 4
    ISSN: 1432-1106
    Keywords: Cooling ; Ventrolateral thalamic nucleus ; Pyramidal system ; Reaction time ; Ballistic movement ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Five cats were trained to perform a forelimb ballistic flexion on a reaction time paradigm including an upper limit of about 400 ms for reinforcement (food pellets). They were implanted with a cyrogenic probe thermically insulated, except at the tip, by a vacuum jacket (outer diameter, 1.1 mm). Four cats had the probe inserted into the ventrolateral thalamic nucleus (VL), contralateral to the moving limb. During cooling they showed increased reaction times, which remained constant throughout daily sessions performed during many weeks, independent of the foreperiod but varying from 25 to 100 ms according to the subject. The temperatures used to upset the reaction times varied from +10 ° C to −8 ° C, depending on the localisation of the probe and on the insulation of the silver tip used to prevent nervous tissue reaction, but for each subject the reaction times always increased when the temperature was lowered. The fifth cat, with a probe inserted between VL and the Centre Median, showed a decrease of reaction times on cooling to 0 ° C and an increase of the reaction times for a cooling at −10 ° C. For one of the four cats with a probe properly inserted into the VL, strain-gauges were stuck on the lever to measure the latency of the decrease of the pressure exerted by the subject when the subject initiated the forelimb flexion in response to the CS. Reaction times and latencies of pressure changes were closely correlated with the movement onset, and they were equally delayed during cooling. This result demonstrates that it is not by slowing down movement velocity that reaction times are upset during VL cooling but by delaying the movement onset.
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  • 5
    ISSN: 1432-1106
    Keywords: Retractor bulbi motoneurones ; Accessory abducens nucleus ; 6th nerve ; Oculomotricity ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Motoneurones innervating the retractor bulbi muscle in the cat have been identified by retrograde labelling with horseradish peroxidase, by intracellular recording and by intracellular staining with horseradish peroxidase. Their somata are found in an accessory abducens nucleus, analogous to that described in some other species, which consists of a narrow column of cells situated in the lateral tegmental reticular field, above the superior olive and medial to the facial nerve. This column of cells extends over approximately 1.5 mm from P 5.5 to P 7. The retractor bulbi motoneurones number from 80 to 120 and have large, elongated somata which give rise to five or six major dendrites. Their axons cross the reticular formation in a dorso-medial direction to pass through the principal abducens nucleus before turning to leave the brain stem in the 6th nerve. Antidromic latencies ranged from 0.4 to 0.7 ms. Some retractor bulbi motoneurones could also be activated antidromically by stimulation of the lateral rectus muscle nerve.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 35 (1979), S. 25-36 
    ISSN: 1432-1106
    Keywords: Retinal ganglion cells ; Cat ; Contrast reversal stimulus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A contrast reversal (alternating phase) stimulus was used to study the responses of 150 retinal ganglion cells from 15 adult cats. Because the majority of the cells did not show perfect linear spatial summation, a ratio of the firing rates at two time periods was used to express the degree of nonlinearity. Y-cells showed a high degree of nonlinearity, and their mean null ratio was significantly lower than that of X-cells. With the stimulus at the null position, X-cells had an unmodulated discharge rate which was significantly higher than maintained activity, while the firing rate of Y-cells was lower than maintained activity. With the stimulus placed at an eccentric position in the receptive field, X-cells responded in a sustained manner, while Y-cells respond transiently. Because of these observations, we conclude that X-cells correspond to the sustained cells, while Y-cells correspond to the transient cells.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 35 (1979), S. 161-175 
    ISSN: 1432-1106
    Keywords: Cerebral cortex ; Superior colliculus ; Cat ; Horseradish peroxidase method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The retrograde labeling of cortical neurons with horseradish peroxidase (HRP) was used to investigate the morphological features of neurons in various cortical areas projecting to the superior colliculus in the cat. Corticotectal cells were found to be labeled in layer V of the entire cerebral cortex. The number of labeled cells and their locations varied according to the sites of injections of HRP in the colliculus. Most of the Corticotectal cells identified in the present study were small (9–20 μm in diameter, 66%) and medium (20–40 urn, 30%) pyramidal neurons and only 4% of them were large (more than 40 μm). The labeled cells, 261 in total number, had somal diameters of 20.8±8.0 μm (mean and SD). The range of sizes of the labeled neurons was different in different cortical areas. For example, the labeled neurons in the Clare-Bishop area had a greater proportion of large diameter cells than in other areas. The present findings are largely in agreement with the previous data of anterograde degeneration methods with respect to the topographical correlation of the Corticotectal projections. However, in some cortical areas, e.g., the sensorimotor and the first visual (area 17) cortex of the lateral surface of the hemisphere, relatively small numbers of Corticotectal neurons appear to have been labeled by retrogradely transported HRP. The sparsity of the labeled neurons in certain cortical areas may reflect the existence of Corticotectal neurons with axon collaterals supplying brain structures other than the superior colliculus.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 35 (1979), S. 269-285 
    ISSN: 1432-1106
    Keywords: Cerebral cortex ; Pontine nuclei ; Cat ; Horseradish peroxidase method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Horseradish peroxidase (HRP) injections in various portions of the cat pontine nuclei resulted in retrograde labeling of neurons in layer V of the ipsilateral cerebral cortex. Corticopontine neurons, pyramidal in type, have been found to be labeled in the entire cortex, confirming the previous findings of anterograde degeneration studies. Most (91%) of the labeled cells were 14–26 μm in diameter (mean 19.4±4.5 μm SD). Small (10–20 μm) and medium (20–40 μm) cells represent 51.5% and 47.7%, respectively, of the total number of the labeled neurons. The populations of the neurons of various sizes were almost identical in different cortical areas, and were different from the populations of corticoreticular and corticospinal cells. Corticopontine cells were well labeled in experimental cases of 3-days' survival time, confirming the topographical organization established previously by degeneration studies for this projection system. However, in cases of shorter survival time (20–27 h), the number of labeled neurons was very small. The relative paucity of labeled Corticopontine neurons in the sigmoid and lateral gyri is discussed with reference to other cortical descending neurons (e.g., the corticotectal, corticoreticular and corticospinal) which have hitherto been identified morphologically as well as physiologically.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 35 (1979), S. 395-406 
    ISSN: 1432-1106
    Keywords: Cat ; Spinal cord ; Phrenic motoneurons ; Neuron geometry ; Horseradish peroxidase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Cat phrenic motoneurons, labeled by intradiaphragmatic injection of horseradish peroxidase, formed a tight cluster in the most ventral portion of the ventral horn in lamina IX of the lower cervical cord. Cell counts were symmetrically distributed for 17 to 21 mm along the longitudinal axis of the cord with a unimodal peak at the junction of segments C5 and C6. The phrenic nucleus was bilaterally organized on either side of the cord with anatomical symmetry and in no case was there evidence for the crossing of phrenic axons in the cord. Assessment of cellular geometry and intercellular relationships demonstrated that phrenic cell diameters approximated a normal distribution with a single peak at 26 μm while longitudinal cell lengths averaged 76 μm. Cells of different size were mixed randomly at all levels of the nucleus. The minimum distance between cells was about 10 μm and the maximum cell packing density approached 2 cells per 106 μm3. The results confirm the location of the cat phrenic nucleus, extend the knowledge of phrenic motoneuronal geometry, and provide an anatomical basis for the understanding of recruitment and synchronization phenomena within the phrenic nucleus.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 35 (1979), S. 465-477 
    ISSN: 1432-1106
    Keywords: Cat ; Monkey ; Lateral geniculate nucleus ; Visual nondominant suppression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We have studied the suppression of firing in single LGN cells of cat and monkey in response to visual stimulation of the nondominant eye. In the cat LGN most of the cells of each of the main laminae show this nondominat suppression. X cells having their dominant input from the ipsilateral eye were suppressed to a significantly greater degree than any other cell type in the cat LGN. In the monkey LGN nondominant suppression was absent in all 19 X-like cells studied, whereas 6 of 21 Y-like cells showed nondominant suppression. Thus nondominant suppression is present in the magnocellular laminae of the monkey LGN, where the Y-like cells are found, but appears to be absent from the parvocellular laminae, where the X-like cells are found.
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  • 11
    Electronic Resource
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    Springer
    Experimental brain research 35 (1979), S. 479-494 
    ISSN: 1432-1106
    Keywords: Thermosensitivity ; Lesions ; Spinal cord ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The behavioural thermosensitivity of cat paws was examined before and/or after restricted uni- and/or bilateral lesions had been made in the spinal cord between the first and fifth cervical segments. Unilateral lesions of the lateral funiculus, which involved at least its whole width at the level of the central canal, reproducibly were found to interfere with the contralateral sensitivity for temperature increases and/or decreases. No corresponding thermosensory deficiencies were found after unilateral lesions involving the ventral spinal quadrant or the dorsal funiculus. Various bilateral and combined lesions were made, but no cat ever developed thermoanaesthesia. The bilateral lesions included bilateral transections of: the middle parts of the lateral funiculi, the dorsal halves of the lateral funiculi, the dorsal funiculi, and the ventral spinal half. Most of our knowledge about peripheral behavioural thermosensitivity after spinal cord injury is based on observations of human patients, especially after anterolateral chordotomies. The present finding of contralateral thermosensory deficiencies after lesions of the middle part of the lateral funiculus fits with some of the clinical reports. The present failure to cause thermoanaesthesia, on the other hand, is inconsistent with the theory of a single ascending spinal pathway for behavioural thermo-sensitivity, which has emanated mainly from the clinical observations.
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  • 12
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    Springer
    Experimental brain research 35 (1979), S. 495-510 
    ISSN: 1432-1106
    Keywords: Pretectal nuclei ; Superior colliculus ; Visual response pattern ; Retinal input types ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Single unit recordings from 220 units were obtained from the nuclei praetectalis anterior (NPA) and posterior (NPP) of 30 immobilized, anesthetized cats. Quantitative analysis of pretectal (PT) visual activity was mainly based on recordings from the NPP. For comparison, 160 collicular (CS) neurons were studied. A strong sensitivity for moving objects was evident in both samples. The following main types of PT activity were categorized: (A) slow movement, direction-selective units (21%); (B) slow movement, nondirection-selective units (19%); (C) units nonselective for stimulus velocity and direction (24%); (D) jerk movement selective, nondirection-selective units (36%). Latency measurements following single shocks to optic chiasm (OX) and tract (OT) showed mainly slow conducting fiber input to the PT and CS which can be divided into two different groups by conduction properties and synaptic delay: direct W-input and delayed W-input. Fast Y-fiber input of both types, direct and indirect, was recorded at both sites, PT and CS.
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  • 13
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    Experimental brain research 36 (1979), S. 191-194 
    ISSN: 1432-1106
    Keywords: Hypercomplex cells ; Area 18 ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Single unit recording has revealed the same orientation sensitive cell classes in cat area 18 as are to be found in area 17. These include particularly the various types of hypercomplex cell belonging to the S, C, and B cell families.
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  • 14
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    Springer
    Experimental brain research 36 (1979), S. 285-300 
    ISSN: 1432-1106
    Keywords: VL nucleus ; Single units ; Reaction time ; Movement initiation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Unrestrained cats performed ballistic forelimb flexion movements triggered by an auditory stimulus (CS) on a simple reaction time (RT) paradigm. During the variable foreperiod the subject was required to hold down a lever and to release it on presentation of the CS. The RTs ranged from 200 to 300 ms. The activity of single neurons of the ventrolateral nucleus of the thalamus (VL) was recorded bilaterally. More than 40% of the 166 units recorded in the VL contralateral to the performing limb presented, after the CS, changes of activity with a latency less than 100 ms and were classified into three types: (1) Twenty-five units had a short latency transient increase of activity 10 to 30 ms after the CS, followed by a longer increase or decrease in activity. Short latency increase as well as subsequent increase of the firing rate were not correlated to the RTs. (2) Twenty-nine units showed a 40–60 ms latency increase of activity which lasted long enough to continue during the forelimb movement. These units displayed a correlation between the RTs and the mean firing rate measured in the 40–100 ms period after the CS. The more the cells were activated, the shorter the RTs. (3) Fifteen units presented a reciprocal pattern of discharge with respect to the type (2) units. The firing rate decreased with latencies ranging from 20 to 90 ms after the CS. Only 14,5% of the 96 units recorded in the VL ipsilateral to the performing limb presented changes of activity starting in the 100 ms period following the CS. Background firing levels as well as phasic activity were rather low compared to those observed contralaterally. Sixteen units showed burst activity while the cat was performing but burst pattern was not time-related to the task. In an unconditioned animal, a very low level of activity and an absence of modulations were observed in both VLs.
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  • 15
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    Springer
    Experimental brain research 37 (1979), S. 41-47 
    ISSN: 1432-1106
    Keywords: Eye alignment ; Cat ; Visual experience ; Maturation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In the developing kitten, the alignment of the pupils changes from strongly divergent to almost parallel. The visual axes, however, seem to stay almost parallel throughout this period. The influence of early visual experience on this development is examined in the present study. The results suggest that the development of eye alignment is not controlled by visual experience, but depends on maturational processes, and that normal visual input serves only to halt these processes at the appropriate time.
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  • 16
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    Springer
    Experimental brain research 37 (1979), S. 177-181 
    ISSN: 1432-1106
    Keywords: Cat ; Autoradiography ; Abducens nucleus ; Primary vestibular fibers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Primary vestibular projections to the ipsilateral abducens nucleus were found in cats by injecting anterograde tracer substances (radioactive proline and fucose) into Scarpa's ganglion. Labelling was observed in the rostral and middle portion of the abducens nucleus.
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  • 17
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    Springer
    Experimental brain research 37 (1979), S. 405-416 
    ISSN: 1432-1106
    Keywords: Cerebellum ; Purkinje Cells ; Splanchnic mechanoreceptors ; Cat ; Cervelet ; Cellules Purkinje ; Mécanorécepteurs splanchniques ; Chat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Les activités simple et complexe de cellules de Purkinje du cervelet du Chat (zone vermienne des lobules V et VI) ont été enregistrées au moyen de microélectrodes extracellulaires. Ces réponses étaient obtenues par stimulation de différents types de mécanorécepteurs du tractus gastro-intestinal: récepteurs musculaires connectés à des fibres C, récepteurs péritonéaux de mouvement connectés à des fibres Aγδ ou B, corpuscules de Pacini connectés à des fibres Aβ. Les caractéristiques des fibres splanchniques projetant sur cette aire cérébelleuse ont été définies. Des convergences splanchno-somatiques, splanchno-viscérales et splanchno-corticales ont été mises en évidence.
    Notes: Summary Climbing and mossy fibre activity in Purkinje cells of cat cerebellum (vermis part of lobules V and VI) were recorded by means of extracellular microelectrodes. Responses were obtained by stimulation of different types of mechanoreceptors in the gastro-intestinal tract: muscular receptors connected with C fibres, peritoneal movement receptors connected with Aγδ or B fibres, Pacinian corpuscules connected with Aβ fibres. The characteristics of the splanchnic fibre projections on this cerebellar area were defined. Splanchno-somatic, splanchno-visceral, and splanchno-cortical convergences were demonstrated.
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  • 18
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    Springer
    Experimental brain research 37 (1979), S. 609-613 
    ISSN: 1432-1106
    Keywords: Orientation subunits ; Visual cortex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The orientation domain in the cortical visual areas of anesthetized cats has been investigated by employing the 14C-Deoxyglucose technique (Sokoloff et al., 1977). Orientation subunits (OS) are seen in the first (V1), the second (V2) and the third visual area (V3) as well as in the visual areas of the suprasylvian sulcus. In the latter regions OS are less elaborated than in V1, V2, and V3. The OS are continuous through all cortical layers; in V1 however, only weak label is detected in layer 4C. In V1, V2, and V3 the width of the OS is about 0.4 mm and the average distance between two OS centers is 0.9 mm. The spatial pattern of the OS seems to be more regular in the visual field periphery than in regions representing the vertical meridian.
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  • 19
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    Anatomy and embryology 155 (1979), S. 323-331 
    ISSN: 1432-0568
    Keywords: Telencephalon ; Choroid plexus ; Lateral ventricle ; Blood vessels ; Micro Corrosion cast ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Corrosion casts of the complete vascular network of the choroid plexus of the lateral ventricle in the cat brain were studied in SEM using the injection-replication method. The villi of this plexus are located only on its supero-anterior and infero-posterior parts, being most densely packed in the former region, close to the interventricular foramen. The capillaries of the villi display small nodular thickenings, which suggest the presence of small, sinusoidal dilatations. The main vessel supplying the plexus with blood is the anterior choroidal artery. The plexus is also characterized by a particularly rich venous network, which is drained by a prominent (main) choroid vein. The vascular organization of the choroid plexus of the lateral ventricle in cat is compared to that of the corresponding plexuses in other mammals.
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  • 20
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    Acta neuropathologica 48 (1979), S. 55-58 
    ISSN: 1432-0533
    Keywords: Lafora-like bodies ; Morphogenesis ; Glycogen metabolism ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Lafora-like bodies in an 8-year-old cat were studied light and electron microscopically and histochemically. In addition to Lafora-like bodies composed of branching filaments, glycogen granules and electron-dense materials, abnormal accumulations of glycogen granules attracted attention. The most remarkable features were the developmental processes of the branching filaments originating directly from glycogen granules. Lafora-like bodies in the present study showed ultrastructural, histochemical, and enzymatic similarities to those described in the previous reports in Lafora's disease, glycogenosis and other cases. From these results, a certain disturbance of the glycogen metabolism is considered to be probably related to the productive mechanism of Lafora-like bodies.
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  • 21
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    Experimental brain research 34 (1979), S. 197-200 
    ISSN: 1432-1106
    Keywords: Claustrum ; Visual cortex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Visual cortex, including areas 17, 18, and sometimes 19, was injected with tritiated leucine. Terminal labelling could be detected by autoradiography in the dorsocaudal part of the ipsilateral claustrum in all cases.
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  • 22
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    Experimental brain research 34 (1979), S. 241-261 
    ISSN: 1432-1106
    Keywords: Locomotion ; Central generator ; Cat ; Deafferentation ; Spinal cord
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A central network of neurones in the spinal cord has been shown to produce a rhythmic motor output similar to locomotion after suppression of all afferent inflow. The experiments were performed mainly in acute spinal cats (th. 12), which had received DOPA i.v. and the monoamine oxidase inhibitor Nialamide. In some preparations all dorsal roots supplying the spinal cord were transected, in others phasic afferent activity was suppressed by curarization. The activity was recorded as neurograms from nerve filaments or as electromyograms. It is concluded that: 1. alternating activity between flexors and extensors of foot, ankle, knee, and hip of one limb can still occur 2. the duration of the flexor discharges vary less with the cycle duration than the extensor discharges 3. different flexor muscles may retain individual patterns 4. the activity at different joints can be dissociated 5. there is at least one network for each limb 6. the coordination between the two hindlimbs can be alternating as in walking or be more closely spaced as in galloping 7. alternating activity in the ankle remains even when only segments L6, L7 and S1 are intact.
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  • 23
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    Pflügers Archiv 382 (1979), S. 51-55 
    ISSN: 1432-2013
    Keywords: Cerebellectomy ; Vestibuloocular reflex ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The effects of cerebellectomy on the semi-circular canal evoked responses recorded from individual vertical and oblique eye muscles were studied in cats anesthetized with Ketamine. The phase lag relative angular acceleration of the electromyographic response was consistantly smaller over the frequency range tested (0.02–1.0 Hz) in cerebellectomized than in intact animals. This finding indicates that the time constant of the central, neural integrator was shifted towards smaller values by the lesion. This was also suggested when the vertical eye movements generated by rotation about the pitch axis were recorded in the fully alert animal. In addition, the EOG data show that the phase of the VOR in the low frequency range was not altered following cerebellectomy suggesting that the macular influences were still present. When the EMG responses of the superior oblique (SO) and superior rectus (SR) muscles were studied in their presumed main mode, i.e. roll-canal and pitch-canal, respectively, no difference was noted in hemicerebellectomized animals when compared to intact control animals. However, when SO and SR were studied in pitch-canal and roll-canal rotation, respectively, dramatic changes in the response pattern were noted in lesioned animals.
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  • 24
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    Psychopharmacology 63 (1979), S. 151-153 
    ISSN: 1432-2072
    Keywords: Discriminative stimulus properties ; Psychomotor stimulants ; Cat ; d-Amphetamine ; Clozapine ; Cocaine ; Morphine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cats were trained to choose between two levers of an operant chamber using interoceptive cues provided by d-amphetamine or saline as the discriminative stimuli. Following training, stimulus generalization was observed to additional doses of d-amphetamine and cocaine, but not to morphine. Clozapine blocked the generalization of the drug discrimination response to d-amphetamine, but had no effect on generalization to cocaine. These data indicate that discriminative stimulus properties of psychomotor stimulants, previously described in rats, are similar in cats.
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  • 25
    ISSN: 1432-0878
    Keywords: Thalamus ; Horseradish peroxidase ; Golgi-impregnation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Afferent connections to the ventrobasal complex (VB) of the thalamus were studied by means of retrograde transport of horseradish peroxidase (HRP) and by the Golgi-method. After HRP-injection into the VB, peroxidase-positive cells were observed contralaterally in the dorsal column nuclei (DCN), in the trigeminal nuclei and in the lateral cervical nucleus (LCN), and ipsilaterally in the somatosensory I (SI) and II (SII) cortical areas. Labeled cells of different shape and size were compared with neurons impregnated by the Golgi-technique. On the basis of HRP-labeling it is concluded that cells projecting to the VB are different in size and shape even within one region and that they correspond to the relay or efferent neurons observed in the Golgimaterial.
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  • 26
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    International ophthalmology 1 (1979), S. 109-122 
    ISSN: 1573-2630
    Keywords: Photocoagulation ; Non-linear effects ; Physics ; Morphology ; Nd glass Q-switched laser ; Scanning electron microscopy ; Chamber angle ; Monkey
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Working at a power density above optical breakdown threshold, irradiation effects upon the angle of the anterior chamber of the Macaca speciosa monkey by a Nd glass Q-switched laser, have been analysed with scanning electron microscopy. Two different damage effects can be identified: openings of Schlemm's canal and the creation of a cyclodialysis, that is opening the uveoscleral outflow routes; the latter may be a more effective one than the former. Also a third mechanism, namely a structural alteration of the trabecular meshwork, at the molecular level by laser action, has been inferred. The physical effects leading to optically induced mechanical damage are discussed. Applicability of such effects upon the morphological findings described here, is limited and to a greater part speculative. A better definition of the physical parameters, required for optimal therapeutical damage effects in the treatment of the wide angle glaucoma may be obtained by trial and error methods, which are guided by the results of electron microscopical analyses of samples obtained from in vivo and in vitro experiments.
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  • 27
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    European archives of oto-rhino-laryngology and head & neck 222 (1979), S. 113-118 
    ISSN: 1434-4726
    Keywords: Brain-stem electric response (BSER) ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The early auditory evoked responses have been studied in bilaterally hearing cats, and in animals with hereditary unilateral anacusis. Cross-over stimulation of the hearing ear occurs at an interaural attenuation of 50-50 dB, and all six waves of the responsare present at supra-threshold stimulus levels.
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  • 28
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    Cell & tissue research 196 (1979), S. 117-122 
    ISSN: 1432-0878
    Keywords: Vasopressin neurons ; Oxytocin neurons ; Immunocytochemistry ; Magnocellular neuroendocrine system ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Our immunocytochemical investigation of the magnocellular neuroendocrine cells in the cat hypothalamus reveals a mixture of vasopressin (VP)- and oxytocin (OT)-containing neurons in the supraoptic (NSO), the paraventricular (NPV) and in five accessory nuclei (NAC). We describe the lateral hypothalamic nucleus (NLH), a new accessory nucleus, lying at the junction of the internal capsule and pallidum, and possibly involved in drinking behavior. Previously characterized incompletely in mammals, the four other accessory nuclei consist of the circularis (NC), anterior fornical (NAF), posterior fornical (NPF) and retrochiasmatic (NRC). The two peptidergic cell types, VP and OT, are equally mixed in the NPV and the NAC, but in the NSO VP neurons predominate. The perikarya of these VP and OT neurons do not show distinct morphological differences at the level of light microscopy. The organization of magnocellular neurosecretory neurons in the cat hypothalamus closely resembles that described in other mammals with the exception of the unique presence of the lateral hypothalamic accessory nucleus.
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  • 29
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    Cell & tissue research 196 (1979), S. 175-179 
    ISSN: 1432-0878
    Keywords: Thalamo-cortical projection ; Anteroventral nucleus ; HRP retrograde transport ; Golgi impregnation ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Neurons displaying a thalamo-cortical projection were marked by means of the retrograde transport of horseradish peroxidase (HRP), and the labeled elements were compared with neurons impregnated by the Golgi technique. Injections of HRP into the posterior area of the limbic cortex resulted in its uptake by various anterior thalamic nuclei, especially the anteroventral nucleus. HRP-positive cells are characterized by their position, dendritic orientation, and the shape and size of their somata. On the basis of the combined HRP- and Golgi-analysis three different types of thalamo-cortical relay neurons can be distinguished.
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  • 30
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1-23 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new calculation of the vibrational frequencies of poly(ethy1 ethylene) based on the actual molecular geometry was performed. The calculation takes into account new experimental data such far-infrared spectra and Raman spectra of the stretched polymer, infrared spectra of poly(ethyl ethylene)-(2,2;d2) (P-4-1-d2) and poly(ethyl ethylene)-(3,3,4,4;d4) (P-4-1-d4), and Raman spectra of poly(ethyl ethylene)-(1,3,3;d3) and poly(ethyl ethylene)-(3,3,4,4;d4). Refinement produced a set of force constants; it is also applicable to poly(propyl ethylene).
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  • 31
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The vibrational analysis of modification I of poly(propyl ethylene), poly(propyl ethylene)-(2,2;d2), and poly(propyl ethylene)-(1,2,2;d3) has been performed using the valence force field derived for poly(ethyl ethylene) and the actual molecular geometry. The band assignments are based on infrared polarization and Raman data.
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  • 32
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 55-62 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The nucleation and growth of the crystalline core in the row structures of isotactic polystyrene were investigated by transmission electron microscopy. The number of core crystals, nucleated at a specific temperature, depends on the external strain. Their length was found to increase with time if the sample is kept at the straining temperature. If a strained sample is cooled to room temperature and subsequently reheated, no further growth of the core crystals is observed. Obstacles in the path of growth were circumvented by local changes of the growing direction. Melt-soluble noncrystallizable molecules are rejected by the growing core into the surrounding melt. The observations suggest a growth mechanism of the cores based on the successive self-induced alignment of molecules at the tip of the growing cores.
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  • 33
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 45-53 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Carbon-13 spin-lattice relaxation times (T1), nuclear Overhauser enhancements (NOE), and resonance linewidths (Δp) have been measured for a series of terephthalic acid polyesters containing ethyl, butyl, hexyl, and isopropyl groups between neighboring terephthalate units. The relaxation parameters of all carbons in the terephthalate groups are independent of the length of the separating alkyl chain. Reduced NOE's are seen for all carbons. The data are interpreted in terms of a log X2distribution of correlation times of constant width, but variable average mobility. The average mobility in the alkyl chain increases with increasing distance from the terephthalate group in a given polymer. For a given position in the chain. mobility increases with increasing chain length. This behavior is consistent with the presence of independently reorienting, highly solvated terephthalate groups.
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  • 34
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 73-79 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polytetrafluoroethylene (PTFE) was extruded from a capillary rheometer at temperatures between the first-order transition at 30°C and the melting point. Both PTFE at 50-300°C and various smectic states of certain low-molecular benzylidene anilines obey the following relationship between the shear stress τ and the apparent shear rate $ \dot \gamma :{\rm }\tau = K\dot \gamma ^{{1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} $. The apparent viscosities for the two classes of substances are similar even though their molecular weights differ by a factor of about 104. Both have characteristic shear planes which are parallel to the polymer chains in PTFE and normal to the long axes of the benzylidene aniline molecules. The melting process in virgin PTFE begins near 300°C. Above this temperature, the shear stress at constant shear rate increases and the rheological exponent rises from 0.25 toward 0.5 at the final melting point.
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  • 35
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 63-71 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent experiments have supported the view that polyethylene (PE) single crystals kept in suspension, in a variety of liquids, have different physical properties compared with the same crystals after drying. The present work was undertaken in an attempt to directly measure one of the basic properties of crystals in suspension, namely their percent crystallinity (X). Differential scanning calorimetry was chosen as the primary tool for this investigation. A method has been developed to determine the weight of PE in a suspension of crystals in a nonsolvent. Thus, a determination of X can be made. For suspension crystals, X was found to be at least 88.5%, some 6% larger than that for the corresponding dried or freeze-dried material. Implications with regard to the fold-surface structure are discussed. Differences in degree of crystallinity as a function of drying procedure have also been observed.
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  • 36
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 19-26 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of methyl methacrylate photosensitized by several alkyl ketones has been investigated. It was found that alkyl ketones can induce the free radical polymerization of the monomer with an efficiency that increases when the triplet lifetime decreases. For ketones of similar triplet lifetime those decomposing predominantly by a type I photocleavage show greater initiation efficiencies than those that react by a type II mechanism. The results obtained show that quenching of the excited ketones by the monomer does not induce polymerization. For ketones bearing γ-hydrogens the initiation is due to the 1,4-biradical produced by intramolecular hydrogen abstraction.
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  • 37
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 49-58 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of γ irradiation on a series of vinyl polymers, which included polymethacrylonitrile, poly(α-chloroacrylonitrile), poly(dimethyl itaconate), poly(acrylic anhydride), and poly(methacrylic anhydride), was studied as part of a program to develop improved positive lithographic resists. Radiation-induced degradation was observed for polymethacrylonitrile, poly(α-chloroacrylonitrile), and poly(methacrylic anhydride). Molecular weight degradation as a function of dose was monitored by membrane osmometry or GPC techniques. For γ-irradiated poly(dimethyl itaconate) and poly(acrylic anhydride) crosslinking was found to predominate over chain scission. [G(s)-G(x)] values, calculated from molecular weight inverse versus dose curves, indicate that both nitrile polymers degraded more efficiently than a poly(methyl methacrylate) reference standard on the basis of Mn changes. The radiation behavior of the first three polymers confirms earlier findings than vinyl polymers with quaternary carbons predominantly degrade when subjected to ionizing radiation.
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  • 38
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 97-109 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The triethylamine-initiated polymerization of glycine-NCA [N-carboxylic acid anhydrides (oxazolidine-2,5-diones)], L-alanine-NCA, and sarcosine-NCA, as well as the pyridine-initiated polymerization of sarcosine-NCA, were carried out in the presence of potential cocatalysts. The 11 electrophilic reagents tested in this work can be divided into two classes: N-acyllactams and similar compounds, which are less reactive than the monomers and have no influence on the polymerization; and isocyanates and N-acyl-NCAs or -NTAs [N-thiocarboxylic acid anhydrides (thiazolldine-2,5-diones)], which are more electrophilic than the monomers and behave as cocatalysts in the case of glycine-NCA and alanine-NCA, since their base-initiated polymerization proceeds via the attack of NCA anions on the electrophilic N-acyl NCA chain and (“activated monomer mechanism”). In the case of sarcosine-NCA, however, the propagation involves a nucleophilic chain end (“carbamate mechanism”) and the strong electrophilic reagents behave as inhibitors.
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  • 39
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 139-145 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of poly(vinyl chloride) (PVC) with superoxide anion was carried out in tetrahydrofuran (THF) at 40°C in a nitrogen atmosphere. Remarkable changes in infrared (IR) spectra of the samples treated with superoxide anion were observed in the following regions: ca. 3300, 1680, 1620, and 765 cm-1, which suggested the formation of hydroxyl groups, α,β-unsaturated ketone groups, and ethylenic structures. Ultraviolet-visible spectra also showed the formation of polyene structures. The content of chlorine in the polymer decreased and that of oxygen increased with reaction time. The reaction mechanism was discussed on the basis of these results.
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  • 40
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 155-162 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To determine the content of trans-gauche-trans (TGT) conformation in poly(ethylene glycol) (PEG) 1H-NMR spectra were measured with tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-1,4,6-octanedinato)europium(III) [Eu(fod)3] as a shift reagent. As a result the peaks assigned to the ethylene protons in the polymeric segments separated from those assigned to four ethylene protons as the “near-end” groups, and the singlet peak in the former at the lowest field was assigned to the TGT conformation of the COCCOC sequence. It was confirmed that the conformation of the polymeric segments in PEG complexed with Eu(fod)3 remained unchanged with benzene-d6 content as the solvent. The concentration of TGT conformation increased with the number-average molecular weight (Mn): it increased rapidly until about 70% at Mn = 1500.
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  • 41
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 173-184 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: γ-Ray-induced polymerizations of ferrocenylmethyl methacrylate (FMMA) in crystalline and amorphous states were investigated with kinetical and ESR methods. In the crystalline state the polymerization of FMMA proceeded slowly and gave low-molecular-weight polymers, whereas in the amorphous state it proceeded rapidly and gave polymers of much higher molecular weight. Molecular weight distributions of these polymers were binodal. The temperature dependence and the dose-rate dependence of the polymerization rates were different between the two states. Wide-line nuclear magnetic resonance (NMR) spectra of the amorphous monomer suggested that the polymerization proceeded in a supercooled state. Electron spin resonance (ESR) spectra of γ-irradiated FMMA and 1,1′-ferrocenyl-di(methyl methacrylate) showed that ferrocene radicals and methacrylic radicals were formed simultaneously at low temperature; with increasing temperature the former radicals disappeared, whereas the latter changed into growing chain radicals. The yields of radicals were relatively low; this means that ferrocene groups in the monomers behave as a radiation energy absorber.
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  • 42
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 215-224 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found that carbon disulfide copolymerizes with N-(β-cyanoethyl) ethylenimine by using water as a catalyst. The copolymerization was conducted in detail by using water as a catalyst in the temperature range between 0 and 50°C with various initial concentrations of carbon disulfide and N-(β-cyanoethyl)ethylenimine in the absence of solvent. The copolymer obtained was always composed of the two monomers: 1:1 ratio, independent of the initial concentration of the monomers. The copolymer was white solid material soluble in dimethyl sulfoxide, insoluble in other usual organic solvents and decomposed at 155°C. Spectroscopic analysis of the copolymer combined with the results of elemental analysis indicates that the copolymer had the following structure:
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  • 43
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 267-269 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 44
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 255-266 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alternating polyampholytes (MA-VA) containing two acidic groups and one basic group were prepared by the copolymerization of maleic anhydride (M1) and N-vinylsuccinimide (M2) at 60°C with AIBN as the initiator, followed by acid hydrolysis with 1N hydrochloric acid at 140°C for 24 hr. The monomer reactivity ratios r1 and r2 are 0.025 and 0.06, respectively. The structure of polymers was discussed on the basis of the data of their elementary, infrared (IR), and thermal analyses and the binding ability of heavy metal ion. Polyampholytes were soluble in strong acidic and basic media but were precipitated in the pH range 3-4. An isoelectric point at pH 3 was determined by potentiometric titration and the turbidimetric method. By thermal treatment above 205°C the polyampholyte turned quantitatively into a cyclized lactam. This suggests that the polyampholyte MA-VA has an intramolecular hydrogen bond between the amino and γ-carboxyl groups. The binding of Cu2+ and Hg2+ by the polyelectrolyte was evaluated by equilibrium dialysis.
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  • 45
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 203-213 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Detailed results of the overall thermal degradation of poly(butylene terephthalate) are reported. Laser microprobe analysis and dynamic mass spectrometric techniques were used to identify the primary volatile degradation products and initial pyrolysis reactions that control polymer degradation. A complex multistage decomposition mechanism was observed which involves two major reaction pathways. Initial degradation occurs by an ionic decomposition process that results in the evolution of tetrahydrofuran. This is followed by concerted ester pyrolysis reactions that involve an intermediate cyclic transition state and yield 1,3-butadiene. Simultaneous decarboxylation reactions occur in both decomposition regimes. Finally, the latter stages of polymer decomposition were characterized by evolution of CO and complex aromatic species such as toluene, benzoic acid, and terephthalic acid. Activation energies of formation for the main pyrolysis products were determined from the dynamic measurements of the major ion species and indicate values of E = 27.9 kcal/mole for the production of tetrahydrofuran and E = 49.7 kcal/mole for the production of butadiene.
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  • 46
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 225-236 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article deals with studies of the dilute solution properties of methyl methacrylate-acrylonitrile (MMA-AN) copolymer of 0.415 mole fraction (mf) of acrylonitrile composition. Mark - Houwink parameters for this copolymer have been evaluated in acetonitrile (MeCN), 2-butanone (MEK), dimethyl formamide (DMF), and γ-butyrolactone (γ-BL). The Mark-Houwink exponent a in all four solvents at all temperatures is larger than the corresponding values of the parent homopolymers. The solvent power is in the order of DMF 〈 γ-BL 〈 MEK 〈 MeCN; [η] decreases with an increase in temperature, which is behavior characteristic of polymers in good solvent. The unperturbed dimensions (K0) values, obtained by the Stockmayer-Fixman method, are lower than those for the parent homopolymers and depend on solvent as well as temperature. The solute - solvent interaction parameter X1 values are close to 0.5; X1 is independent of temperature. The excess interaction parameter XABvalues are negative. The results for this copolymer system in regard to low second virial coefficient A2, large X1, and high a values suggest that the large extension of these copolymer chains is due to the unusual short-range interactions.
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  • 47
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 245-254 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (2-Ethyl-2-methyl-1,3-dioxolan-4-yl)methyl- and (2-methyl-2-phenyl-1,3-dioxolan-4-yl) methyl acrylates were synthesized and polymerized. The photochemical behavior of the resulting polymers was investigated to determine whether the polymers pending on the 1,3-dioxolane structure were readily crosslinked with ultraviolet (UV) irradiation. The degree of crosslinking was estimated by the weight-loss method by immersion in acetone, with the result that the polymer with an aromatic substituent was more photocrosslinkable than the polymer that bore the aliphatic substituent. The catalytic effect on photocrosslinking of polymers was also studied by using benzoin and cobalt naphthenate. The infrared (IR) spectra of polymers irradiated in air that showed the new band at 3450 cm-1 were attributed to a hydroxyl group; however, the spectra of polymers irradiated in vacuum displayed little absorption at 3450 cm-1. To explain the mechanism of crosslinking model compounds were prepared and irradiated with UV light. It was concluded that crosslinking proceeds mainly from the fission of the 1,3-dioxolane ring and the coupling of the yielding radicals, together with autooxidation by atmospheric oxygen.
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 281-286 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 49
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 301-312 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Behavior of the free radical copolymerization of N-β-methacryloyloxyethyl derivatives of adenine with that of thymine was studied in chloroform solution, taking account of the specific base-base interaction of these monomers. Hydrogen bonding interaction between such monomers was observed by NMR spectroscopy. The acceleration of copolymerization was found to be greater either at lower monomer concentration or at lower polymerization temperature. When N-β-methacryloyloxyethylcarbazole was used as a comonomer, the rate of copolymerization showed a similar trend as in the case of usual free radical copolymerizations. From r1 and r2 values obtained, the copolymerization was found to be alternating, particularly in the case of copolymerization between monomers having complementary nucleic acid bases. The results suggest that the hydrogen bonding interaction between adenine and thymine plays a role in the propagation step.
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  • 50
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 385-392 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benzaldehyde (PhCHO) is found to be able to initiate the radical polymerization of methyl methacrylate (MMA). The rate of polymerization is expressed by the following equation: Rp = const[PhCHO]0.5[MMA]1.5. The overall activation energy is estimated to be 56.3 kJ mole-1. The mechanism of polymerization is discussed.
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  • 51
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 351-363 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: “Pyran” copolymer, the 2:1 regularly alternating cyclocopolymer (DVE - MA) of maleic anhydride (MA) and divinyl ether (DVE), first discovered in 1951, has been investigated extensively, both from the standpoint of its chemical structure and its biological activity. Although certain aspects of its structure remain to be determined, it has been shown to possess a wide spectrum of biological activity. It possesses antitumor activity and has been investigated clinically. During the clinical investigation, it was found to be an interferon inducer. Interferon is a protein which appears to be the body's first line of defense against viral infection. DVE - MA also possesses antiviral, antibacterial, antifungal, antiarthritic, and anticoagulant properties, activates macrophages, inhibits reverse transcriptase, and is capable of elimination of Pu. During the course of investigations in these laboratories, many structural modifications of DVE - MA have been made. Many of these modifications also possess considerable antitumor activity and interferon-induction capability. Perhaps the most interesting structural modification has been the incorporation of 5-fluorouracil (5-FU) into the polymer (NSC 255083). This polymer has shown (T/C)% [= ratio of test (T) to control (C) survival times] = 189 for dose by intraperitoneal injection of 200 mg/kg animal weight in CD2F1 mice (6/6 survivors after fifth day) against P388 lymphocytic leukemia. This article describes the synthesis of both the monomer and copolymer, and a study of the hydrolytic rate of release of 5-FU from the polymer.
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  • 52
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 377-384 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,2,4-Trimethyl-3-on-1-pentyl methacrylate (TMPM) was first synthesized from the condensation reaction of 2,2,4-trimethyl-1-pentanol-3-on with methacrylic acid. Second, the polymerization of TMPM and the copolymerization of TMPM with styrene (St) were carried out in benzene at 60°C, using 2,2′-azobisisobutyronitrile (AIBN) as an initiator. As the result of kinetic investigation, the rate of polymerization (Rp) could be expressed by: Rp = k[AIBN]0.5 [TMPM]1.0. Kinetic constants of polymerization of TMPM were obtained as follows: kp/kt1/2 = 0.27 dm3/2 mole-1/2 sec-1/2, 2fkd = 1.23 × 10-5 sec-1, f = 0.73, Cm = 2.6 × 10-5, Cs = 1.1 × 10-5. From the results the reactivity of TMPM was found to be larger than that of methyl methacrylate. The overall activation energy was calculated to be 110 kJ mole-1. The following monomer reactivity ratios and Q, e values were obtained: TMPM(M1) - St(M2): r1 = 1.50, r2 = 0.14, Q1 = 2.63, E1 = 0.45.
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  • 53
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 415-423 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homopolymerization of propylene oxide was first conducted at 80°C in the absence of any solvent by using various metal salts of acetic acid and it was found that Mg(OAc)2, Cr(OAc)3, Mn(OAc)2, Co(OAc)2, Ni(OAc)2, Zn(OAc)2, and Sn(OAc)2 were effective for the polymerization. The copolymerization of propylene oxide and carbon dioxide was next examined by using these effective metal salts of acetic acid as catalysts. Most of these were effective also for the copolymerization. The nature of the polymer obtained was strongly dependent on the catalyst used. Co(OAc)2 and Zn(OAc)2 gave an alternate copolymer of propylene oxide and carbon dioxide, Mg(OAc)2, Cr(OAc)3, and Ni(OAc)2 gave a random copolymer, while Sn(OAc)2 gave a homopolymer of propylene oxide. Then the copolymerization of propylene oxide and carbon dioxide was kinetically investigated in some detail by using Co(OAc)2 as a catalyst. On the basis of the results obtained, a plausible mechanism was proposed for both the homopolymerization of propylene oxide and copolymerization of propylene oxide and carbon dioxide.
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  • 54
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 455-464 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the intermediates in unterminated polymerization reactions were studied. It was found that in a first-order initiation (A) all intermediates accumulate monotonically. In a second-order initiation (B) the first intermediates pass through a maximum, whereas the later ones strictly accumulate. An initiator-started polymerization can follow course A or course B, depending on the initial ratio of the concentrations of the initiator and monomer.
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  • 55
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 473-484 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerizations of l-menthyl vinyl ether (l-MVE) with the monomers, that is, maleic anhydride (MAn), dimethyl maleate (DMM), and dimethyl fumarate (DMFu), were undertaken to obtain optically active copolymers. The optically active l-menthyl group in the side chain of copolymers was removed by the ether cleavage reaction with dry-hydrogen bromide gas. The ethercloven copolymers were still optically active. Hence it was concluded that asymmetric carbon atoms were introduced into the copolymer main chain, the reason given being that l-MVE and comonomers (MAn, DMM, and DMFu) made the stereoselective charge-transfer complex one another and copolymerized stereospecifically. From the results of the measurements of optical rotatory dispersion (ORD) and circular dichroism (CD) for copolymers before and after the ether cleavage reaction, the mode of bond opening for α,β-substituted monomers (MAn, DMM, and DMFu) was discussed and the microstructures of copolymers were prepared.
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  • 56
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 503-516 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stability of PTFE latex prepared in the absence of emulsifier by radiation-induced polymerization was investigated by electrophoresis and conductometric titration. The storage stability depends on total dose rather than dose rate, and the stable latex can be obtained in the region log D 〉 0.026 V1 - 0.6, where D is the total dose (104 rad) and V1 is a polymer concentration in latex (g/liter). The stability increases only during polymerization in the presence of enough TFE monomer. The ζ potential of the latex particles lies in the region from -25 to -50 mV in an as-polymerized state (near pH 3) and from -50 to -65 mV at pH 10. The number of carboxyl end groups and surface charge density were examined by conductometric titration with NaOH and calculation from the G values of radiolysis of water. All the surface charge densities measured by conductometric titration are larger than those calculated from the G values. These results suggest that some acids have been formed on the surface of the particles. The acids may be the carboxyl end groups of polymer chains or hydrofluoric acid (HF) adsorbed on the surface. PTFE particles prepared in this polymerization system are stabilized mainly due to the carboxyl end groups and adsorptions of OH- and HF on the particles.
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  • 57
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 539-550 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamically effective fixed-charge density of mercuric phosphate and carbonate parchment-supported membranes have been evaluated by the most recent method of Nagasawa et al., based on the thermodynamics of irreversible processes and compared with the values obtained by the Kobatake et al. and Teorell - Meyer - Sievers (TMS) methods. Bi-ionic potential (BIP) has also been measured for these membranes with three pairs of electrolyte solutions: KCl—NaCl, KCl—LiCl, and NaCl—LiCl. Theoretical values of BIP have been calculated by using the membrane potential and BIP theories recently developed by Toyoshima et al., based on nonequilibrium thermodynamics. Various parameters have also been evaluated and it was found that the theoretical equation of BIP is applicable to these parchment-supported membranes.
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  • 58
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 571-582 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new techniques for the determination of monomer reactivity ratios in copolymerization under high-pressure conditions have been developed, viz., the “sandwich” and the “quenching” method. Both methods are based on repeated quantitative gas chromatographic analysis of the reaction mixture during the low-pressure stages preceding and succeeding the high-pressure stage, of which the kinetics is under investigation. Application of the “sandwich” method implies the occurrence of reaction during both low-pressure stages and consequently the low-pressure kinetic data are required to obtain the transition points of low to high pressure and vice versa. These points constitute the initial and final conditions of the relevant high-pressure reaction. On the contrary, in the “quenching” method no reaction occurs during the low-pressure stages, owing to the lower temperature and the high activation energy of the initiator decomposition. As a consequence, the initial and final conditions of the high-pressure stage can be determined by a simple averaging procedure. Both methods have been tested for the ethylene - vinyl acetate copolymerization at 62°C and 600 kg/cm2 with tert-butyl alcohol as solvent, and appear to lead to almost identical monomer reactivity ratios, although the “quenching” method is slightly preferred in case of copolymerization reactions. Both methods are particularly valuable when one of the reactants is gaseous or the reaction produces a gas. Further merits and drawbacks of both methods are discussed.
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  • 59
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 613-616 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 60
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 747-757 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In due consideration of the specific base-base interaction that exists between nucleic acid molecules, the free radical polymerization of N-β-methacryloyloxyethyl derivatives of adenine, thymine, and theophylline initiated by azobisisobutyronitrile (AIBN) was studied in the presence of N-β-methacryloyloxyethyl-type polymers which have complementary nucleic acid bases as template polymers. The rate of polymerization of N-β-methacryloyloxyethyladenine was accelerated when poly(N-β-methacryloyloxyethyluracil) or -thymine was present in the polymerization system. The effect of the stereoregularity of the template polymers, as well as polymerization temperature and the sort of solvents used on the rate of polymerization, was studied and discussed in some detail. The results suggest that the interaction between complementary bases plays a role in template polymerization behavior.
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  • 61
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 783-787 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Catalytic actions of various additives were studied in the polycondensation of di(4-nitrophenyl) isophthalate with bis(4-aminophenyl) ether in N-methyl-2-pyrrolidone, and 1-hydroxybenzotriazole (HOBt) was found to be a highly effective catalyst that yielded high-molecular-weight polyamide. In addition to the polycondensation of the 4-nitrophenyl ester, the polymerization of negatively substituted phenyl esters like di(2,4,5-trichlorophenyl) isophthalate was also accelerated by HOBt. For the HOBt-catalyzed aminolysis of esters a bifunctional concerted mechanism that involves an eight-membered transition state was proposed.
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  • 62
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 807-813 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibrium constants of the coordination reaction of chlorodimethylformamide·cobaloxime with 4-vinylpyridine-styrene copolymers (PPS) were determined. The constants for PPS, which contain 20-50% 4-vinylpyridine (4VP) unit, measured about 1.3 × 105 liter/mole larger than those in the pyridine system (6.8 × 104 liter/mole). When the polymer ligand is 4VP homopolymer or contains less than 20% 4VP unit, K values are lower. The rate constants (kf) of the coordination reactions of the cobaloxime with polymer ligands were also measured in dimethylformamide (DMF) and benzene. In DMF kf decreased with an increase in 4VP unit content of the polymer ligand; in benzene it was increased by the 4VP fraction. These results can be explained by the variation in conformation of the polymer chain in each solvent. The effect of the polymer chain on complexation was discussed on the basis of the kinetic data.
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  • 63
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 877-888 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of the 1:2 copolymer of divinyl ether and maleic anhydride was investigated by 13C-NMR spectroscopy. The polymer contains the bicyclic unit composed of one molecule of each monomer and the maleic anhydride unit. The carbon chemical shift for these units was calculated on the basis of the chemical shift of many model compounds. The major peaks of the cyclopolymer prepared in chloroform were consistent with the presence of the symmetrical bicyclic unit with cis junction and the trans monocyclic anhydride unit. The carbonyl carbon spectrum for the copolymer obtained in a mixed solvent of acetone and CS2 suggested the predominant formation of the unsymmetrical bicyclic unit. The polymerization process was discussed on the basis of these results.
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  • 64
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 917-918 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 65
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 905-916 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex formation between a poly(N-β-methacryloyloxyethyl) derivative of adenine with one of thymine or uracil was studied in dimethyl sulfoxide and ethylene glycol mixture by ultraviolet (UV) spectroscopy. For the polymer pairs containing complementary nucleic acid bases both hypochromicity and hyperchromicity were found. Stereoregularity of the polymers, as well as the conditions for measurement of, for example, solvent, temperature, and time, affected the complex formation. Both inter- and intramolecular interaction of polymers in solution were discussed in some detail.
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  • 66
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 923-926 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 67
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 931-934 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 68
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl methacrylate (MMA) and styrene (St) copolymerize in the presence of zinc chloride at 3°C under photoirradiation. The contents of methyl methacrylate in the copolymers obtained at a [ZnCl2]/[MMA] molar ratio of 0.4 are systematically larger than 53 mole %, which is the limiting value at a small feed ratio of methyl methacrylate. The resulting copolymers are confirmed as the sole products and not the mixtures by thin layer chromatography. The effect of dilution of the monomer feed mixture with toluene on copolymer composition suggests that it depends chiefly on the feed concentration of styrene and hardly at all on monomer feed ratios. Copolymerizations are also conducted in the presence of stannic chloride at -17°C under photoirradiation and in the presence of ethylaluminium sesquichloride at 0°C with spontaneous initiation. The contents of methyl methacrylate in both copolymers obtained at feed ratios lower than 60 mole % almost correspond to the 1:1 alternating copolymer and increase systematically with higher feed ratios. The systematic deviations of copolymer composition obtained in the presence of metal halides are reasonably interpreted by the participation of the binary molecular complex composed of metal halide and methyl methacrylate in the polymerization of the ternary molecular complex composed of metal halide, methyl methacrylate, and styrene.
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  • 69
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 889-904 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The process of polyethylene terephthalate (PET) formation in the presence of dicarboxylic acids has been studied. Certain amounts of terephthalic acid (TPA) have two- to threefold accelerating efficiency in the polycondensation process. To elucidate the causes of the acceleration the main reactions leading to PET formation in the presence of dicarboxylic acids have been investigated by the use of models. The evaluation of kinetic and equilibrium parameters obtained for model reactions made it possible to conclude that the influence of carboxyl-containing additives on the apparent rate of polycondensation manifests itself in accelerating direct reactions and facilitating the liberation of the eliminated by-product; that is, ethylene glycol (EG) from the polymer melt. Carboxylic acid acts as a catalyst on the ester interchange of 2-hydroxyethyl ester end groups and thus increases the rate of polymer formation in this reaction 10-40 times. The parallel interaction between the 2-hydroxyethyl ester end group and the carboxyl group of the added acid is also catalyzed by the acid and its rate constant is four times larger than that of the catalytic polycondensation of 2-hydroxyethyl ester end groups. Unlike EG, the reaction water formed in the process is more readily removed from the reaction system and thus promotes the intensification of the process. In addition, the carboxyl groups react with the eliminated EG to decrease its amount and shift the equilibrium toward polymer formation. The investigation of the consequent parallel reactions on models made it possible to draw a conclusion about the higher reactivity of 2-hydroxyethyl esters in the esterification processes. This fact has been explained by strengthening the nucleophilicity of the oxygen atom in the hydroxyl of a 2-hydroxyethyl ester group compared with that of EG; for example, by the formation of an intramolecular cycle involving a hydrogen bond. Simultaneously, it has been found that in the system simulating PET polycondensation in the presence of dicarboxylic acids the reaction mechanism involves the catalysis by a proton formed during the carboxyl group dissociation and accepted by the 2-hydroxyethyl ester group.
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 919-921 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 927-930 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 72
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 935-935 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 73
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 943-947 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heterogeneous polymerization of acrylonitrile photoinitiated by naphthalene is influenced by the polarity of the reaction medium. The rate of initiation increases with the increasing dielectric strength of the reaction medium. A similar trend is observable for Stern-Volmer constants of naphthalene fluorescence quenching by acrylonitrile. The ratio kp/kt1/2 of the rate constant for propagation and termination reactions is not influenced by a change in the polarity of the reaction medium. The effect of viscosity on the value of kp/kt1/2 known for polymerization in a homogeneous medium was not observed in the reaction systems studied.
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  • 74
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  • 75
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1267-1277 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The γ-ray-induced addition reaction of carbon tetrachloride onto syndiotactic 1,2-polybutadiene film and liquid 1,2-polybutadiene was carried out at room temperature. In the film gelation was pronounced and the rate of addition increased as the crystallinity of the polymer decreased. In the liquid gelation, which makes the polymer insoluble in carbon tetrachloride, did not take place, although a definite crosslinking reaction was noticed. In this case the appearance of the product changed from a viscous liquid to a white powder as the reaction proceeded. Its structure was compared with that of chlorinated 1,2-polybutadiene. The addition of carbon tetrachloride to the vinyl group in liquid 1,2-polybutadiene caused an anti-Markownikoff-type reaction and was accompanied by an unexpectedly large vinyl depletion in the polymer. The total decrease in the vinyl group was found to be much larger than that brought about by the addition of carbon tetrachloride. This discrepancy was attributed to a cyclization and crosslinking reaction ascribed to the vinyl group bound by the main chain. Cyclization and crosslinking were less noticeable in the chlorination than in the carbon tetrachloride.
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  • 76
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1353-1366 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Products from the thermal decomposition of a chlorinated aromatic polyamide fabric are described for conditions of pyrolysis and flaming and nonflaming oxidative degradation. Volatile degradation products were identified by gas chromatography-mass spectrometry (GC-MS) and the condensible fraction, by infrared (IR) spectroscopy, high-pressure liquid chromatography (HPLC), and MS. Nonvolatile char was characterized by IR and elemental analysis. Twenty-one compounds were identified as volatile products from pyrolysis at 550°C; the condensible material contained ammonium chloride and at least 22 organic compounds. From volatile compounds produced in flaming oxidative degradation 21 compounds were identified, of which CO, CO2, and H2O were prominent. Nonflaming oxidative degradation at 400 and 550°C produced 11 and 21 volatile identifiable compounds, respectively, and results from experiments at the higher temperature compared favorably with results from the flaming experiments. By comparison of data from this work with those from unchlorinated analogs (described in an earlier article), it is concluded that the incorporation of chlorine into the polymeric structure lowers the temperature for the onset of thermal degradation and alters the type and concentration of thermolytic products. The major degradation products can be explained by a mechanism similar to that proposed for aromatic polyamides with the exception of the formation of substantial amounts of ammonium chloride. It is proposed that the latter is formed by an initial acid-catalyzed hydrolysis reaction which is followed by deammoniation or by an intermolecular process that involves an isoimide intermediate.
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  • 77
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1393-1400 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The redox system of potassium persulfate-thiomalic acid (I1-I2) was used to initiate the polymerization of acrylamide (M) in aqueous medium. For 20-30% conversion the rate equation is \documentclass{article}\pagestyle{empty}\begin{document}$$ R_p = - \frac{{d[{\rm M}]}}{{dt}} = K[{\rm M}][{\rm I}_1]^{1/2} $$\end{document} where Rp is the rate of polymerization. Activation energy is 8.34 kcal deg-1 mole-1 in the investigated range of temperature 25-45°C. Mn is directly proportional to [M] and inversely to [I1]. The range of concentrations for which these observations hold at 35°C and pH 4.2 are [I1] = (1.0-3.0) × 10-3, [I2] = (3.0-7.5) × 10-3, and [M] = 5.0 × 10-2-3.0 × 10-1 mole/liter.
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  • 78
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1411-1418 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated polymerizations of styrene, 2-vinylnaphthalene, and 9-vinylanthracene were compared in sulfolane and acetone solvents in the presence of ZnCl2. The relative orders of polymerization rates and polymerization efficiencies, in both solvents, were 9-vinylanthracene 〉 2-vinylnaphthalene 〉 styrene, with faster rates and higher efficiencies occurring in sulfolane. Data obtained from viscosity and gel permeation chromatography (GPC) studies indicate that the molecular weights of the polymers produced in these systems are extremely low, 〈5000. Chemical composition and infrared (IR) spectral data suggest that abnormal transfer reactions (possibly from solvent) may be occurring in the electroinitiated 9-vinylanthracene polymerizations. The polymerization mechanism appears to be cationic in these monomer-solvent systems with ZnCl2.
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  • 79
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1431-1440 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Butene(2B) copolymerizes with 3-heptene(3H) and 4-methyl-2-pentene(4M2P) by a monomer-isomerization copolymerization mechanism in the presence of TiCl3-(C2H5)3Al catalyst at 80°C to yield the copolymers of 1-olefin units. By comparison, the copolymerization of 1-butene(1B) with 4-methyl-1-pentene(4M1P) was also carried out under similar conditions. The composition of the copolymers obtained from these copolymerizations was determined from the ratios of optical densities D723/D1380 and D1170/D1380 in their infrared (IR) spectra. The apparent monomer reactivity ratios for the monomer-isomerization copolymerization of 2B with 3H and 4M2P, in which the concentration of olefin monomer in the feed was used as 2-olefin, were determined as follows: cis-2B(M1)/3H(M2); r1 = 4.00, r2 = 0.20: trans-2B(M1)/3H; r1 = 3.50, r2 = 0.20; 4M2P(M1)-trans-2B(M2): r1 = 0.05, r2 = 9.0. These results indicate that the isomerization of 2-olefins to 1-olefins was important to monomer-isomerization copolymerization.
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  • 80
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1453-1461 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of 3-methyl-1-butene (3M1B), 2-methyl-2-butene (2M2B), or 2-methyl-1-butene (2M1B) with trans-2-butene (2B) was attempted in the presence of a Ziegler-Natta catalyst. It was found the 3M1B underwent monomer-isomerization copolymerization with 2B to give a copolymer consisting of both 3M1B and 1-butene (1B) units, with an infrared (IR) spectrum in good agreement with that obtained from the copolymerization of 3M1B with 1B under similar conditions. When the apparent copolymerization parameters obtained by a TiCl3-(C2H5)3Al catalyst were compared, the apparent reactivity of 3M1B observed in the 3M1B-2B system was much higher than that in the 3M1B-1B system. However, 2M2B and 2M1B did not undergo monomer-isomerization copolymerization with 2B, and only the homopolymer of 1B was obtained under similar conditions.
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  • 81
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1573-1581 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Macrocyclic polyether or crown ether ester derivatives of acrylic and methacrylic acid were synthesized and polymerized. The cation binding properties of the polymers determined by extraction of picrate salts were similar to those obtained for poly(crown ether)s derived from styrene. In the presence of a crown-complexable cation both polymers form insoluble polysalt complexes with sodium carboxymethylcellulose, potassium poly(styrene sulfonate), and potassium polyacrylate. The extent of precipitation depends on the type and concentration of cation as well as on the ratio polyanion to poly(crown ether). The precipitate appears to have an equal number of positive and negative charges. An insoluble hydrogen-bonded complex is formed in the absence of salt when poly(vinylbenzo-18-crown-6) and poly(acrylic acid) are mixed in 0.01M HCl. Organic solutes bound to the poly(crown ether)s, which occur in an aqueous mixture of poly(vinylbenzo-18-crown-6) and picrate anions, are precipitated with the poly(crown ether) when the polysalt complex is formed.
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  • 82
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1595-1604 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of enantiomerically enriched t-butyl thiirane was studied. The stereoelectivity and the kinetic behavior are not changed when a monomer of an initial enantiomeric composition lower than a defined limit value is used. When the enantiomeric composition is higher than this value, the stereoelectivity increases. In agreement with kinetic results, a mechanism is proposed involving, in a first step, the complexation of monomer on preexisting sites of the initiator with formation of highly selective chiral active species on which propagation occurs.
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  • 83
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1557-1563 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 84
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1565-1568 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 85
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxyfluorination and postfluorination behaviors of poly(vinylidene fluoride) films, as well as hydrolysis of the films treated so far, have been studied by infrared (IR) spectrometry. By exposing the polymer film to a mixture of oxygen and fluorine at about 90°C acyl fluoride groups attendant on the scission of the polymer chains were formed. The oxyfluorinated molecules could be further perfluorinated with fluorine alone at about 90°C, leaving many of the acyl fluoride groups. When the properly oxyfluorinated and postfluorinated film was further treated with a hot 6M sodium hydroxide solution the opaque layer of perfluoroalkyl sodium carboxylate of high molecular weight was formed on the surface of the film, to about 3 μm in thickness, which behaved as a cation exchanger. This new type of cation exchanger of perfluoroalkyl carboxylic acid was significantly more acidic than the usual methacrylic acid exchanger. It was able to adsorb the sodium ions from a neutral sodium chloride solution up to about 70% of the exchange capacity and to keep the ions stable while washing them with water, though it could be regenerated to the hydrogen form with a dilute acetic acid solution. The nature of the new ion exchanger has been examined in some detail by IR spectrometry with Li+, Na+, and Cs+ ions.
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  • 86
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1583-1593 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereoelective polymerization of racemic t-butyl thiirane was performed with chiral zinc glycolate. Monomers and polymers of high optical purities were isolated. A new kinetic scheme in which the ratio of the rates of consumption of both enantiomers obeys a second-order relationship is proposed. This behavior is different from that observed for other three-membered ring monomers.
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  • 87
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1739-1758 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft copolymers of nucleic acid bases and L-α-amino acids on polyethyleneimine were synthesized, and carboxyl derivatives of adenine and thymine were grafted by the p-nitrophenyl ester method onto linear and branched polyethyleneimine. The carboxyl derivatives of nucleic acid bases were also grafted onto the monomeric graft copolymers of L-α-amino acids on polyethyleneimine; the carboxyl derivatives were obtained by the condensation of polyethyleneimine with L-α-amino acids with a coupling agent.
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  • 88
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1727-1737 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The growth center in the anionic polymerization of methacrylic esters is stabilized with alkaline alkoxides, sodium tert-butoxide in particular. The lifetime of the growth center was investigated in the polymerization of methyl methacrylate by evaluating yield and molecular weight distribution of the polymer formed when the monomer was added in two doses. The average lifetime of the original growth center stabilized by sodium tert-butoxide at 20°C under the given conditions was longer than several minutes. The stabilization of the growth center was also used in the stepwise copolymerization of n-butyl methacrylate and methyl methacrylate. The copolymer thus obtained in high yield was characterized as a block copolymer on the basis of its solubility, nuclear magnetic resonance (NMR) spectra, and measurements of the complex shear modulus.
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  • 89
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1779-1788 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homogeneous catalyst Re(CO)5X (X = Cl, Br) was found to promote the homopolymerization of terminal alkynes at elevated temperatures. Detection and structure characterization of low-molecular-weight products provided evidence of the formation of a metal-acetylide species as the initiator of polymerization, and propagation occurs by a series of insertion reactions of coordinated alkynes into metal-carbon bonds of the growing chain. Evidence of the active forms of the catalyst comes from studies on gas evolution, catalyst derivatization, and copolymerization reactions. The final polymers have a linear, polyconjugated macrostructure, and the formation of aromatic species was not detected in these reactions.
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  • 90
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1771-1777 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found that N,N,N′,N′-tetramethylethylene diamine and hexamethyl phosphorus triamide minimize chain transfer reactions in the polymerization of 1,3-butadiene in hydrocarbon solvent with alkylsodium or alkylpotassium initiators. The polymers obtained with alkylsodium initiators had a high molecular weight and high vinyl content at 90-95% conversion. The molecular weight of the polybutadiene made by alkylsodium and alkylpotassium initiators was dependent on the polymerization temperatures and modifier ratios, but the vinyl contents were independent of the modifier ratios. Vinyl contents of alkylpotassium-initiated polymers showed a slight dependency on polymerization temperature; the vinyl contents of alkylsodium-initiated polymers were independent of temperature. Addition of lithium tert-butoxide and potassium tert-amylate to these initiators in the presence of the modifiers affected the molecular weight but not the microstructure.
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  • 91
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1795-1800 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymerization of methyl trifluoroacrylate (MTFA) with propylene in bulk was induced by γ irradiation. A wide range of the initial monomer composition gives an equimolar alternating co-polymer. The reactivity ratios of r1 (MTFA) and r2 (propylene) were determined to be 0.01 and 0.005, respectively. The polymerization rate at an equimolar monomer composition is proportional to the 1.0 power of the dose rate. The dose rate dependency of higher than 0.5 may be ascribed to unimolecular termination due to a degradative chain transfer of propagating radicals to propylene. The G values of the initiating radical formation and the polymerization reaction were calculated to be 1.78 and 1336, respectively. The dependence of the copolymerization rate on the temperature was small, and the activation energy of copolymerization was 1.1 kcal/mole from -6 to 50°C.
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  • 92
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1887-1888 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 93
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1911-1921 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: α-Isobutyl-L-aspartate oligomers, Z-(α-i-Bu-Asp)2n-OEt (n = 1-5), where Z = benzyloxycarbonyl and OEt = ethyl ester, were prepared stepwise, and their conformation in solution was investigated by optical rotation, circular dichroism (CD), and NMR spectroscopy. The oligomers up to hexamer existed only in a disordered form. An ordered structure began to appear at octamer and decamer in chloroform and 2,2,2-trifluoroethanol. The ordered structure was more favorable for N-unprotected oligomers, H-(α-i-Bu-Asp)2n-OEt, in comparison with the corresponding Z-(α-i-Bu-Asp)2n-OEt. The effects of oligomer concentration and temperature on the structure were slightly observed. The most likely ordered structure was a β form caused by intramolecular association.
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  • 94
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1963-1976 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thiophene was polymerized in high yield on exposure to aluminum chloride in solvent under mild conditions. Experimental evidence [IR, NMR, UV, and mass spectra, elemental analyses, reductive desulfurization, and comparison with the literature trimer of thiophene (prepared with phosphoric acid)] suggests the following structure: From gel permeation chromatography an average weight of 1290 was obtained, which corresponded to the presence of 15 rings; the highest-molecular-weight chains contained about 192 rings. Mechanistically, participation of cationic intermediates is proposed. Apparently chain extension can occur by various routes, including participation of neutral oligomer molecules.
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  • 95
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1953-1961 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermodynamic parameters for the interaction of the hydrophobic fluorescent probe, 2-p-toluidinylnaphthalene-6-sulfonate (TNS), and polycations that contain a piperidinium cation and various nonpolar pendant groups were calculated. Binding is exothermic and involves a positive entropy gain. The contribution of the entropy term to the free energy change tends to increase with increasing hydrophobicity of the polymers. The intensity of the fluorescence of TNS is enhanced when the probe binds to the polycations. The nature and phenomena of hydrophobic fluorescent probe binding with the polymers are discussed.
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  • 96
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1991-2001 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolysis/mass spectrometric studies have been made on polystyrene, poly(vinyl chloride), and poly(methyl methacrylate) with electron ionization (EI) and chemical ionization (CI) mass spectrometry and a variable temperature probe for direct insertion into the source of the mass spectrometer. Similar results obtained with EI and CI mass spectrometry are in agreement with previous experiments. Advantages of the simplification of spectra in the CI made, as well as the advantages of using both techniques for identification of pyrolysis products, are discussed.
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  • 97
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 2003-2011 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon dioxide was copolymerized with 2-methylaziridine and 1-phenethylaziridine in the presence of organozinc coordination catalysts. Fully alternating copolymers-polyurethanes were obtained. Relations between reaction conditions and polymer yield are given. On the basis of these results a probable scheme of the copolymerization reaction is proposed.
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  • 98
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 193-202 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentiometric titrations in water of high-molecular-weight partly hydrolyzed polyacrylamides were analyzed by the Lifson - Katchalsky rodlike model. A fair concordance was found between theory and experimental curves with pK0 of acid functions of about 4.75 when 0 〈 τ 〈 0.49. Two methods were derived to calculate the parameter n of the extended Henderson-Hasselbach equation by using a series expansion of pKa vs. α, not yet reported in the literature. A new equation for n was established and comparison between two sets of values of n, obtained by using the theoretical ΔpK curves and series expansion is discussed.
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  • 99
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 237-244 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Q-e concept of the Alfrey and Price1 has been applied successfully to the prediction of the pressure effect on the individual reactivity ratios in free-radical copolymerizations. Although the Q value of a given monomer is generally little affected by an increase in pressure, the e value is pressure dependent. The knowledge of the Q and e values at high pressures permits the prediction of variations in reactivity ratios with pressure. Some important consequences have been drawn from this concept.
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  • 100
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 2039-2054 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between tert-butylchloride (t-BuCl) and dimethylcyclopentadienylaluminum (Me2AlCPD) was studied as a model for initiation by the tert-butyl cation (t-Bu⊕) and termination by cyclopentadienylation by the Me2Al(CPD)Cl⊖ counteranion of isobutylene polymerization. All reaction products formed in this model system have been identified and quantitatively determined. A comprehensive scheme that indicates pathways to these products was developed (scheme III). It is proposed that the predominant product, tert-butylcyclopentadiene (t-BuCPD), arises in the collapse of the t-Bu⊕-Me2Al(CPD)Cl⊖ ion pair, mainly by CPD⊖ transfer to the tert-butyl cation. The minor products are neopentane (t-BuMe) and isobutylene (i-C4H8), which are probably formed, respectively, by Me⊖ transfer to and proton loss from the t-butyl cation. Cyclopentadienylation selectivity increases by lowering the temperature and extrapolation of results suggests 100% cyclopentadienylation at -55°C. The t-BuCl/Me2AlCPD ratio strongly influences the overall reaction pathway. The reaction is first order in t-BuCl with ΔEa of ca. 7 kcal/mole (1,2-dichloroethane or chlorobenzene solvents, +24 to -29°C). Indirect evidence indicates that the kinetic product of cyclopentadienylation is 5-t-BuCPD and that this isomer cannot be tert-butylated; that is, the initiation of 5-t-BuCPD polymerization by t-Bu⊕ is sterically unfavorable. Detailed analysis of the chemistry and kinetics of the t-BuCl/Me2AlCPD model system holds important clues to the controlled polymerization of olefins leading to macromolecules with cyclopentadiene (CPD) termini.
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