137 resultados para Urethane


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Poly(ether urethane) cationomers based on poly(oxytetramethylene), 4,4'-bibenzyldiisocyanate, N-methyldiethanolamine as chain extender, and acrylic acid/poly(acrylic acid) as quaternization agent were synthesized. Pyrrole (15 wt.-%) was polymerized in films of the ionomer containing CuCl2. The films were characterized by dynamic mechanical analysis, thermogravimetry and differential scanning calorimetry. The electric conductivity of the film without polypyrrole is 7.5 . 10(-12) Omega(-1)cm(-1), while incorporation of polypyrrole increases the conductivity to 4.5 . 10(-6) Omega(-1) cm(-1).

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In this study we report on the synthesis, kinetic characterization and application of a novel biotinylated and active-site-directed inactivator of cathepsin B. Thus the peptidyliazomethane biotinyl-Phe-Ala-diazomethane has been synthesized by a combination of solid-phase and solution methodologies and has been shown to be a very efficient inactivator of bovine and human cathepsin B. The respective apparent second-order rate constants (k0bs./[I]) for the inactivation of the human and bovine enzymes by this reagent, namely approximately 5.4 x 10(4) M-1 and approximately 7.8 x 10(4) M-1, compare very favourably with those values determined for the urethane-protected analogue benzloxycarbonyl-Phe-Ala-chloromethane first described by Green & Shaw [(1981) J.Biol. Chem. 256, 1923-1928], thus demonstrating that the presence of the biotin moiety at the P3 position is compatible with inhibitor effectiveness. The utilization of this reagent for the detection of cathepsin B in electrophoretic gels, using Western blotting and in combination with a streptavidin/alkaline phosphatase detection system, is also demonstrated. Given that the peptidydiazomethanes exhibit a pronounced reactivity towards cysteine proteinases, we feel that the present label may well constitute the archetypal example of a wide range of reagents for the selective labelling of this class of proteinase, even in a complex biological milieu containing additional classes of proteinases.

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The maximum amount of ethyl carbamate (EC), a known animal carcinogen produced by the reaction of urea and ethanol, allowed in alcoholic beverages is regulated by legislation in many countries. Wine yeast produce urea by the metabolism of arginine, the predominant assimilable amino acid in must. This action is due to arginase (encoded by CARl). Regulation of CARl, and other genes in this pathway, is often attributed to a well-documented phenomenon known as nitrogen catabolite repression. The effect of the timing of di-ammonium phosphate (DAP) additions on the nitrogen utilization, regulation of CARl, and EC production was investigated. A correlation was found between the timing of DAP addition and the utilization of nitrogen. When DAP was added earlier in the fermentations, less amino nitrogen and more ammonia nitrogen was sequestered from the media by the cells. It was also seen that early DAP addition led to more total nitrogen being used, with a maximal difference of ~25% between fermentations where no DAP was added versus addition at the start of the fermentation. The effect of the timing ofDAP addition on the expression of CARJ during fermentation was analyzed via northern transfer and the relative levels of CARl expression were determined. The trends in expression can be correlated to the nitrogen data and be used to partially explain differences in EC formation between the treatments. EC was quantified at the end of fermentation by GC/MS. In Montrachet yeast, a significant positive correlation was found between the timing of DAP addition, from early to late, and the final EC concentration m the wine (r = 0.9226). In one of the fermentations, EC levels of 30.5 ppb was foimd when DAP was added at the onset of fermentation. A twofold increase (69.5 ppb) was observed when DAP was added after 75% of the sugars were metabolized. When no DAP was added, the ethyl carbamate levels are comparable at a value of 38 ppb. In contrast, the timing of DAP additions do not affect the level EC produced by the yeast ECU 18 in this manner. The study of additional yeast strains shows that the effect of DAP addition to fermentations is strain dependent. Our results reveal the potential importance of the timing of DAP addition to grape must with respect to EC production, and the regulatory effect of DAP additions on the expression of genes in the pathway for arginine metabolism in certain wine yeast strains.

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In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

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The work presented in this thesis is regarding the development and evaluation of new bonding agents for short polyester fiber - polyurethane elastomer composites. The conventional bonding system based on hexamethylenetetramine, resorcinol and hydrated silica was not effective as a bonding agent for the composite, as the water eliminated during the formation of the RF resin hydrolysed the urethane linkages. Four bonding agents based on MDI/'I‘DI and polypropyleneglycol, propyleneglycol and glycerol were prepared and the composite recipe was optimised with respect to the cure characteristics and mechanical properties. The flow properties, stress relaxation pattern and the thermal degradation characteristics of the composites containing different bonding agents were then studied in detail to evaluate the new bonding systems. The optimum loading of resin was 5 phr and the ratio of the -01 to isocyanate was 1:1. The cure characteristics showed that the optimum combination of cure rate and processability was given by the composite with the resin based on polypropyleneglycol/ glycerol/ 4,4’diphenylmethanediisocynate (PPG/GL/MDI). From the rheological studies of the composites with and without bonding agents it was observed that all the composites showed pseudoplastic nature and the activation energy of flow of the composite was not altered by the presence of bonding agents. Mechanical properties such as tensile strength, modulus, tear resistance and abrasion resistance were improved in the presence of bonding agents and the effect was more pronounced in the case of abrasion resistance. The composites based on MDI/GL showed better initial properties while composites with resins based on MDI/PPG showed better aging resistance. Stress relaxation showed a multistage relaxation behaviour for the composite. Within the-strain levels studied, the initial rate of relaxation was higher and the cross over time was lesser for the composite containing bonding agents. The bonding agent based on MDI/PPG/GL was found to be a better choice for improving stress relaxation characteristics with better interfacial bonding. Thennogravimetirc analysis showed that the presence of fiber and bonding agents improved the thennal stability of the polyurethane elastomer marginally and it was maximum in the case of MDI / GL based bonding agents. The kinetics of degradation was not altered by the presence of bonding agents

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Els polímers són una sèrie de compostos que troben un ampli ventall d'aplicacions en la indústria actual. Un exemple són les espumes de poliuretà, estructures de tipus cel·lular obtingudes mitjançant la reacció química entre compostos de tipus isocianat i compostos de tipus poliol (polièters amb diferent nombre de grups hidroxil). És imprescindible l'ús d'additius d'estructura tensioactiva (surfactants de silicona) per estabilitzar el procés d'espumació i per proporcionar una estructura cel·lular ordenada i homogènia en mida i distribució. La síntesis i caracterització de les molècules precursores (polihidrosiloxans i polièters al·lílics), l'estudi de la reacció d'hidrosililació com a via d'obtenció dels diferents surfactants per reacció d'addició entre els polihidrosiloxans i els polièters al·lílics i la caracterització i avaluació en formulacions comercials de poliuretà dels surfactants sintetitzats han constituït els objectius del present treball. MEMÒRIA La Tesi Doctoral ha estat presentada seguint el següent esquema: CAPÍTOL I. INTRODUCCIÓ A LA QUÍMICA DEL POLIURETÀ. Es presenten els principis de la química del poliuretà, fent esment dels recents avenços en la síntesis i caracterització d'aquests compostos polimèrics, així com un apartat concret centrat en els surfactants de silicona. Es presenten les estructures habituals d'aquests compostos comercials i es detallen les reaccions de síntesi i les característiques físiques que aquests compostos proporcionen a les espumes de poliuretà. CAPÍTOL II. OBJECTIUS. 1.- Síntesis y caracterització d'una àmplia gamma de poliglicols al·lílics i de polihidrosiloxans amb grups hidrur reactius, ambdós precursors d'estructures polimèriques de tipus surfactant. 2.- Estudi de la reacció d'hidrosililació com a via de formació d'enllaços Si-C no hidrolitzables, mitjançant la reacció d'addició entre els substrats al·lílics insaturats i els polisiloxans amb grups hidrur reactius. 3.- Caracterització de les estructures polimèriques de tipus surfactant sintetitzades i avaluació d'aquestes en formulacions de poliuretà, a fi de relacionar l'estructura química d'aquests oligómers amb els efectes físics que originen en l'espuma de poliuretà. CAPÍTOL III. SÍNTESI I CARACTERITZACIÓ DE SUBSTRATS AL·LÍLICS INSATURATS DE TIPUS POLIGLICOL. S'han caracteritzat per HPLC-UV una sèrie de polietilenglicols comercials. S'ha estudiat la reacció de derivatització al·lílica sobre els grups hidroxil dels polièters comercials (PEG, PPG i copolímers PEG-PPG) i s'han caracteritzat exhaustivament els productes sintetitzats (1H,13C-RMN, GC, GC-MS, FTIR, ESI-MS, HPLC-UV). S'ha iniciat un estudi de polimerització aniònica sobre nous epòxids amb un punt de diversitat molecular, sintetitzant-se i caracteritzant-se els corresponents nous polièters obtinguts. CAPÍTOL IV. SÍNTESI I CARACTERITZACIÓ DE POLIHIDROSILOXANS REACTIUS. S'estudia la síntesis de polihidrosiloxans amb grups hidrur reactius, mitjançant la reacció de polimerització aniònica d'obertura d'anell ("AROP, anionic ring opening polimerization") i mitjançant la reacció de polimerització per equilibració catiònica. Es presenta una caracterització exhaustiva dels productes sintetitzats i es descriu la naturalesa de la microestructura polimèrica a partir de la distribució bivariant dels copolímers PDMS-co-PHMS (poli(dimetilsiloxà)-co-poli(hidrometilsiloxà)). CAPÍTOL V. ESTUDI SISTEMÀTIC DE LA REACCIÓ D'HIDROSILILACIÓ. S'ha estudiat la reacció d'hidrosililació amb la finalitat de sintetitzar estructures copolimèriques poliglicol-polisiloxà a partir de la reacció de polisiloxans hidrur reactius i polièters al·lílics. S'han provat diferents catalitzadors (Pt/C 5%, cat. de Speier i cat. de Karstedt), s'han sintetitzat diferents estructures tensoactives (lineals i ramificades) i s'ha modelitzat les diferents reaccions secundàries observades, per presentar un estudi mecanístic de la reacció d'hidrosililació aplicada a la síntesis de molècules d'elevat PM a partir de la reacció entre substrats al·lílics insaturats i polihidrosiloxans. CAPÍTOL VI. AVALUACIÓ DELS SURFACTANTS EN FORMULACIONS DE POLIURETÀ. S'ha estudiat la idoneïtat dels surfactants de silicona sintetitzats en diferents formulacions de poliuretà comercials. S'ha relacionat el comportament físic d'aquests surfactants en les espumes de poliuretà amb la seva estructura química a partir de l'anàlisi per microscòpia electrònica de rastreig. CAPÍTOL VII. CONCLUSIONS. S'han esposat les conclusions extretes de cada capítol.

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This paper details the synthesis, characterisation and physical analyses of a series of hydrogen bonded urethane supramolecular polymer systems that are created by a facile one-step synthesis from inexpensive and commercially available starting materials. We report the synthesis and characterisation of a series of low molecular weight bisurethanes (<650 a.m.u.) that exhibit physical properties in the bulk that are characteristic of polyurethane materials possessing far higher molecular weight. The physical characteristics of these low molecular weight bisurethanes were investigated by using temperature-dependent rheological analysis and viscometry and the nature in which these compounds assembled was assessed using IR and NMR spectroscopies. These studies reveal that these simple bisurethanes self-assemble via hydrogen bonding interactions.

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The present paper details the synthesis, characterization, and preliminary physical analyses of a series of polyisobutylene derivatives featuring urethane and urea end-groups that enable supramolecular network formation to occur via hydrogen bonding. These polymers are readily accessible from relatively inexpensive and commercially available starting materials using a simple two-step synthetic approach. In the bulk, these supramolecular networks were found to possess thermoreversible and elastomeric characteristics as determined by temperature-dependent rheological analysis. These thermoreversible and elastomeric properties make these supramolecular materials potentially very useful in applications such as adhesives and healable surface coatings.

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A series of six low molecular weight elastomers with hydrogen bonding end-groups have been designed, synthesised and studied. The poly(urethane) based elastomers all contained essentially the same hard block content (ca. 11%) and differ only in the nature of their end-groups. Solution state 1H NMR spectroscopic analysis of model compounds featuring the end-groups demonstrate that they all exhibit very low binding constants, in the range 1.4 to 45.0 M-1 in CDCl3, yet the corresponding elastomers each possess a markedly different nanoscale morphology and rheology in the bulk. We are able to correlate small variations of the binding constant of the end-groups with dramatic changes in the bulk properties of the elastomers. These results provide an important insight into the way in which weak non-covalent interactions can be utilized to afford a range of self-assembled polyurethane based materials that feature different morphologies.

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The electrospinning of urethane based low molecular weight polymers differing only in the nature of the hydrogen bonding end-groups has been investigated. For the end-groups with the lowest binding constants at maximum solubility only droplets, are produced at the electrode; in contrast, increasing the binding constant of the end-group results in electrospun fibres being produced. The properties of the fibres produced are subject to changes in solvent, concentration and temperature. Typical diameters for these fibres were found to be some 10 s of μm, rather than the sub-micron dimensions often produced in electrospinning systems. Such diameters are related to the high initial concentrations required; this also may influence the rate of solvent removal and preferential surface solidification which feature in these examples. A simple theoretical model is used to relate the association constant to the molecular weight required for fibre formation; significantly lower levels of association are required for higher molecular weight macromonomers compared to smaller molecular systems.

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Characterization of neural and hemodynamic biomarkers of epileptic activity that can be measured using noninvasive techniques is fundamental to the accurate identification of the epileptogenic zone (EZ) in the clinical setting. Recently, oscillations at gamma-band frequencies and above (N30 Hz) have been suggested to provide valuable localizing information of the EZ and track cortical activation associated with epileptogenic processes. Although a tight coupling between gamma-band activity and hemodynamic-based signals has been consistently demonstrated in non-pathological conditions, very little is known about whether such a relationship is maintained in epilepsy and the laminar etiology of these signals. Confirmation of this relationship may elucidate the underpinnings of perfusion-based signals in epilepsy and the potential value of localizing the EZ using hemodynamic correlates of pathological rhythms. Here, we use concurrent multi-depth electrophysiology and 2- dimensional optical imaging spectroscopy to examine the coupling between multi-band neural activity and cerebral blood volume (CBV) during recurrent acute focal neocortical seizures in the urethane-anesthetized rat. We show a powerful correlation between gamma-band power (25–90 Hz) and CBV across cortical laminae, in particular layer 5, and a close association between gamma measures and multi-unit activity (MUA). Our findings provide insights into the laminar electrophysiological basis of perfusion-based imaging signals in the epileptic state and may have implications for further research using non-invasive multi-modal techniques to localize epileptogenic tissue

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High explosives are highly sensitive to accidental detonation by impact, fire, shrapnel and small arms fire. This sensitivity can be reduced by storing the energetic material within a rubbery polymer matrix and are known as plastic bonded explosives (PBX). The current procedure used to manufacture PBX involves mixing the energetic material with a hydroxy-functionalised aliphatic polymer. Upon the addition of an isocyanate crosslinker an immediate polymerisation occurs and thus the rapidly curing mixture must be used to fill the missile or shells, referred to as ‘stores’. This process can lead to poor distribution of the crosslinker resulting in the formation of an inhomogeneously crosslinked matrix and the formation of voids. One solution to this problem involves containing the crosslinker within polyurethane microcapsules that are uniformly dispersed in the explosive-polymer mixture. Upon the application of a stimulus the crosslinker can be released from the microcapsules and the formation of a uniformly crosslinked PBX achieved. Herein is reported the design and synthesis of polyurethane microcapsules that release isocyanate crosslinkers when desired using a thermal stimulus. This has been achieved by exploiting the thermally-reversible nature of oxime-urethane and Diels-Alder adducts that have been incorporated into the shell wall of the microcapsules. An alternative approach to controlling the polymerisation of PBX materials has also been achieved using thermally-reversible blocked isocyanates that regenerate the isocyanate crosslinker when exposed to heat.

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The caudal pressor area (CPA) is a brainstem area located close to the spinal cord. The activation of the CPA increases sympathetic activity and mean arterial pressure (MAP) by mechanisms dependent on the commissural nucleus of the solitary tract (commNTS) and rostroventrolateral medulla, however, the signals that activate the CPA to produce these responses are still unknown. Therefore, in the present study, we investigated the activity of glutamatergic and GABAergic mechanisms from the CPA and commNTS in rats exposed to hypoxia and the effects of the inhibition of CPA neurons on cardiorespiratory responses to peripheral chemoreceptor activation with i.v. sodium cyanide (NaCN). Male Sprague-Dawley rats (250-280 g, n=5-8/group) were used. In conscious rats, most of the commNTS neurons (66 +/- 11%) and part of the CPA neurons (36 +/- 7%) activated by hypoxia (8% O2) were glutamatergic (contained VGLUT2mRNA). Small part of the neurons activated during hypoxia was GABAergic (contained GAD-67mRNA) in the commNTS (9 +/- 4%) or the CPA (6 +/- 2%). In urethane anesthetized rats, the inhibition of CPA neurons with bilateral injections of muscimol (GABA-A agonist, 2 mM) reduced baseline MAP, splanchnic sympathetic nerve discharge (SND) and phrenic nerve discharge (PND). Muscimol into the CPA also reduced by around 50% the pressor and sympathoexcitatory responses and the increase in PND to peripheral chemoreceptor activation with NaCN (50 mu g/kg i.v.), without changing sympathetic baroreflex responses. These data suggest that CPA mechanisms facilitate cardiorespiratory responses to peripheral chemoreflex activation. Immunohistochemistry results also suggest that at least part of the CPA mechanisms activated by hypoxia is glutamatergic. (C) 2011 IBRO. Published by Elsevier Ltd. All rights reserved.

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A rise in arterial PCO(2) stimulates breathing and sympathetic activity to the heart and blood vessels. In the present study, we investigated the involvement of the retrotrapezoid nucleus (RTN) and glutamatergic mechanisms in the Botzinger/C1 region (Botz/C1) in these responses. Splanchnic sympathetic nerve discharge (sSND) and phrenic nerve discharge (PND) were recorded in urethane-anesthetized, sino-aortic-denervated, vagotomized, and artificially ventilated rats subjected to hypercapnia (end-expiratory CO(2) from 5% to 10%). Phrenic activity was absent at end-expiratory CO(2) of 4%, and strongly increased when end-expiratory CO(2) reached 10%. Hypercapnia also increased sSND by 103 +/- 7%. Bilateral injections of the GABA-A agonist muscimol (2 mM) into the RTN eliminated the PND and blunted the sSND activation (Delta = +56 +8%) elicited by hypercapnia. Injections of NMDA receptor antagonist AP-5 (100 mM), non-NMDA receptor antagonist 6,7-dinitro-quinoxaline-2,3-dione (DNQX; 100 mM) or metabotropic glutamate receptor antagonist (+/-)-alpha-methyl-4-carboxyphenylglycine (MCPG; 100 mM) bilaterally into the Botz/C1 reduced PND (Delta = +43 +/- 7%, +52 +/- 6% or +56 +/- 11%, respectively). MCPG also reduced sSND (Delta = +41 +/- 7%), whereas AP-5 and DNQX had no effect. In conclusion, the increase in sSND caused by hypercapnia depends on increased activity of the RTN and on metabotropic receptors in the Botz/C1, whereas PND depends on increased RTN activity and both ionotropic and metabotropic receptors in the Botz/C1.

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Inhibitory neurotransmission has an important role in the processing of sensory afferent signals in the nucleus of the solitary tract (NTS), particularly in spontaneously hypertensive rats (SHR). In the present study, we tested the hypothesis that gamma-aminobutyric acid (GABA) mediated neurotransmission within the NTS produces an inhibition of the baroreflex response of splanchnic sympathetic nerve discharge (sSND). In urethane-anesthetized, artificially ventilated and vagotomized male SHR and Wistar Kyoto (WKY) rats we compared baroreflex-response curves evoked after bilateral injections into the NTS of the GABA-A antagonist bicuculline (25 pmol/50 nl) or the GABA-B antagonist CGP 35348 (5 nmol/50 nl). Baseline MAP in SHR was higher than the WKY rats (SHR: 153+/-5, vs. WKY: 112+/-6 mm Hg, p<0.05). Bilateral injection of bicuculline or CGP 35348 into the NTS induced a transient (5 min) reduction in MAP (Delta = -26+/-4 and -41+/-6 mm Hg, respectively vs. saline Delta = +4+/-3 mm Hg, p<0.05) and sSND (Delta = -21+/-13 and -78+/-7%, respectively vs. saline: Delta = +6+/-4% p<0.05). Analysis of the baroreceptor curve revealed a decrease in the lower plateau (43+/-11 and 15+/-5%, respectively vs. saline: 78+/-6%, p<0.05) and an increase in the sympathetic gain of baroreflex (6.3+/-0.3, 7.2+/-0.8% respectively vs. saline: 4.2+/-0.4%, p<0.05). Bicuculline or CGP35348 into the NTS in WKY rats did not change MAP, sSND and sympathetic baroreflex gain. These data indicate that GABAergic mechanisms within the NTS act tonically reducing sympathetic baroreflex gain in SHR. Crown Copyright (C) 2010 Published by Elsevier By. All rights reserved.