955 resultados para Alpha spectroscopy on plated samples


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Dans la première partie, nous présentons les résultats de l'étude du supraconducteur sans inversion de symétrie LaRhSi3 par spectroscopie muonique. En champ nul, nous n'avons pas détecté de champ interne. Ceci indique que la fonction d'onde de l'état supraconducteur n'est pas dominée par l'état triplet. Les mesures en champ transverse de 35G présentent une transition en accord avec la transition de phase attendue sous le champ critique Hc1. Nous avons répété ces mesures pour un champ entre Hc1 et Hc2, 150G. Le spectre obtenu pour ces mesures conserve l'asymétrie et relaxe rapidement à basse température tel que prédit pour un supraconducteur dans la phase d'Abrikosov. Néanmoins, les relaxations produites par ce balayage en température présentent une transition à près de 2 fois la température critique attendue. Dans la deuxième partie de ce mémoire, nous donnons l'interprétation des résultats de la diffraction neutronique inélastique par l'étude des champs électriques cristallins. Ces mesures ont été effectuées sur des aimants frustrés SrHo2O4 et SrDy2O4 sous la forme de poudre. L'étude des niveaux produits par les champs cristallins par la méthode des opérateurs de Stevens indique une perte du moment cinétique dans les deux matériaux. Pour le SrDy2O4, l'état fondamental serait constitué de quatre états dégénérés quasi accidentellement qui portent un moment magnétique total non-nul. Toute fois, nos mesures de susceptibilité magnétique ne montrent aucun ordre au-dessus de 50mK. Pour le SrHo2O4, le fondamental est formé d'une paire accidentelle. Nous obtenons un moment magnétique de 6.94(8)$\mu_B$ ce qui s'accorde avec les données expérimentales.

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Objectif—Comparer les effets de la stérilisation au plasma de gaz de peroxyde d’hydrogène (HPGP) à l’oxyde d’éthylène (EO) et à la vapeur (ST) sur les propriétés physico-chimiques et d’adhésion bactérienne de fils de nylon et de polyéthylène. Design expérimental—Etude in vitro. Matériel—Des brins non stérilisés, stérilisés au HPGP, à l’EO et ST; de fil nylon leader (FNL), de fil de nylon pêche (FNP) et de fil de polyéthylène (PE) ont été utilisés. Méthodes—Une analyse de surface au spectroscope photo-électronique à rayons X (XPS), une mesure de l’angle de contact, une analyse par microscopie à force atomique (AFM) et l’adhésion bactérienne de Staphylococcus intermedius et d’Escherichia Coli ont été testés sur les brins. Résultats—Une oxydation de la surface de tous les échantillons stérilisés a été observée quelque soit la méthode de stérilisation. La stérilisation a augmenté significativement l’angle de contact pour tous les types de fil quelque soit la méthode. La rugosité n’a pas été affectée significativement par la méthode de stérilisation pour le FNL et FNP. L’adhésion bactérienne a été affectée significativement par la méthode de stérilisation. Le PE a un angle de contact, une rugosité et une adhésion bactérienne significativement plus élevée que le FNL et FNP, peu importe la méthode de stérilisation. Conclusion—La stérilisation au HPGP constitue une alternative intéressante à la vapeur et l’EO. Le PE n’est peut être pas un matériel idéal par sa capacité d’adhésion bactérienne. De futures études sont nécessaires pour déterminer la signification clinique de ces trouvailles.

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Les azapeptides sont des mimes peptidiques où le carbone alpha d’un ou de plusieurs acides aminés est remplacé par un atome d’azote. Cette modification tend à stabiliser une conformation en repliement beta en raison de la répulsion électronique entre les paires d’électrons libres des atomes d’azote adjacents et de la géométrie plane de l’urée. De plus, le résidu semicarbazide a une meilleure résistance face aux protéases en plus d’être chimiquement plus stable qu’une liaison amide. Bien que les propriétés des azapeptides en fassent des mimes peptidiques intéressants, leurs méthodes de synthèses font appel à la synthèse laborieuse d’hydrazines substituées en solution. Le peptide sécréteur d’hormone de croissance 6 (GHRP-6, His-D-Trp-Ala-Trp-D-Phe-Lys-NH2) est un hexapeptide synthétique qui possède une affinité pour deux récepteurs distincts: les récepteurs GHS-R1a et CD36. Les travaux effectués au cours de mon doctorat qui seront détaillés dans cet ouvrage visent à atteindre deux objectifs: (1) le développement d’analogues du peptide GHRP-6 sélectif à un seul récepteur et (2) la mise au point d’une nouvelle méthodologie pour la synthèse combinatoire d’azapeptides. En réponse au premier objectif, la synthèse parallèle de 49 analogues aza-GHRP-6 a été effectuée et certains candidats sélectifs au récepteur CD36 ont été identifiés. L’étude de leurs propriétés anti-angiogéniques, effectuée par nos collaborateurs, a également permis d’identifier des candidats intéressants pour le traitement potentiel de la dégénérescence maculaire liée à l’âge. Une nouvelle approche pour la synthèse combinatoire d’azapeptides, faisant appel à l’alkylation et la déprotection chimiosélective d’une sous-unité semicarbazone ancrée sur support solide, a ensuite été développée. La portée de cette méthodologie a été augmentée par la découverte de conditions permettant l’arylation régiosélective de cette sous-unité semicarbazone, donnant accès à treize nouveaux dérivés aza-GHRP-6 possédant des résidus aza-arylglycines aux positions D-Trp2 et Trp4. L’élaboration de conditions propices à l’alkylation et la déprotection chimiosélective de la semicarbazone a donné accès à une variété de chaînes latérales sur l’acide aminé « aza » préalablement inaccessibles. Nous avons, entre autres, démontré qu’une chaîne latérale propargyl pouvait être incorporée sur l’acide aminé « aza ». Tenant compte de la réactivité des alcynes, nous avons ensuite élaboré des conditions réactionnelles permettant la formation in situ d’azotures aromatiques, suivie d’une réaction de cycloaddition 1,3-dipolaire sur support solide, dans le but d’obtenir des mimes de tryptophane. Sept analogues du GHRP-6 ont été synthétisés et testés pour affinité au récepteur CD36 par nos collaborateurs. De plus, nous avons effectué une réaction de couplage en solution entre un dipeptide possédant un résidu aza-propargylglycine, du paraformaldehyde et une variété d’amines secondaires (couplage A3) afin d’accéder à des mimes rigides d’aza-lysine. Ces sous-unités ont ensuite été incorporées sur support solide afin de générer sept nouveaux azapeptides avec des dérivés aza-lysine à la position Trp4 du GHRP-6. Enfin, une réaction de cyclisation 5-exo-dig a été développée pour la synthèse de N-amino imidazolin-2-ones en tant que nouveaux mimes peptidiques. Leur fonctionnalisation par une série de groupements benzyliques à la position 4 de l’hétérocycle a été rendue possible grâce à un couplage Sonogashira précédant la réaction de cyclisation. Les propriétés conformationnelles de cette nouvelle famille de composés ont été étudiées par cristallographie aux rayons X et spectroscopie RMN d’un tétrapeptide modèle. L’activité biologique de deux mimes peptidiques, possédant un résidu N-amino-4-méthyl- et 4-benzyl-imidazolin-2-one à la position Trp4 du GHRP-6, a aussi été examinée. L’ensemble de ces travaux devrait contribuer à l’avancement des connaissances au niveau des facteurs structurels et conformationnels requis pour le développement d’azapeptides en tant que ligands du récepteur CD36. De plus, les résultats obtenus devraient encourager davantage l’utilisation d’azapeptides comme peptidomimétiques grâce à leur nouvelle facilité de synthèse et la diversité grandissante au niveau de la chaîne latérale des acides aminés « aza ».

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Photoconductivity (PC) processes may be the most suitable technique for obtaining information about the states in the gap. It finds applications in photovoItaics, photo detection and radiation measurements. The main task in the area of photovoltaics, is to increase the efficiency of the device and also to develop new materials with good optoelectronic properties useful for energy conversion, keeping the idea of cost effectiveness. Photoconduction includes generation and recombination of carriers and their transport to the electrodes. So thermal relaxation process, charge carrier statistics, effects of electrodes and several mechanisms of recombination are involved in photoconductivity.A major effect of trapping is to make the experimentally observed decay time of photocurrent, longer than carrier lifetime. If no trapping centers are present, then observed photocurrent will decay in the same way as the density of free carriers and the observed decay time will be equal to carrier lifetime. If the density of free carriers is much less than density of trapped carriers, the entire decay of photocurrent is effectively dominated by the rate of trap emptying rather than by the rate of recombination.In the present study, the decay time of carriers was measured using photoconductive decay (PCD) technique. For the measurements, the film was loaded in a liquid Helium cryostat and the temperature was controlled using Lakshore Auto tuning temperature controller (Model 321). White light was used to illuminate the required area of the sample. Heat radiation from the light source was avoided by passing the light beam through a water filter. The decay current. after switching off the illumination. was measured using a Kiethely 2000 multi meter. Sets of PCD measurements were taken varying sample temperature, sample preparation temperature, thickness of the film, partial pressure of Oxygen and concentration of a particular element in a compound. Decay times were calculated using the rate window technique, which is a decay sampling technique particularly suited to computerized analysis. For PCD curves with two well-defined regions, two windows were chosen, one at the fast decay region and the other at the slow decay region. The curves in a particular window were exponentially fitted using Microsoft Excel 2000 programme. These decay times were plotted against sample temperature and sample preparation temperature to study the effect of various defects in the film. These studies were done in order to optimize conditions of preparation technique so as to get good photosensitive samples. useful for photovoltaic applications.Materials selected for the study were CdS, In2Se3, CuIn2Se3 and CuInS2• Photoconductivity studies done on these samples are organised in six chapters including introduction and conclusion.

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This thesis lays importance in the preparation and characterization of a few selected representatives of the ferrite family in the nanoregime. The candidates being manganese zinc ferrite and cobalt ferrite prepared by coprecipitation and sol-gel combustion techniques respectively. The thesis not only stresses importance on the preparation techniques and optimization of the reaction conditions, but emphasizes in investigating the various properties namely structural, magnetic and electrical. Passivated nickel nanocomposites are synthesized using polystyrene beads and adopting a novel route of ion exchange reduction. The structural and magnetic properties of these magnetic nanocomposites are correlated. The magnetocaloric effect (MCE) exhibited by these materials are also investigated with a view to finding out the potential of these materials as magnetic refrigerants. Calculations using numerical methods are employed to evaluate the entropy change on selected samples.

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Polyaniline is chemically synthesised and doped with camphor sulphonic acid. FTIR studies carried out on these samples indicate that the aromatic rings are retained after polymerisation. The percentage of crystallinity for polyaniline doped with camphor sulphonic acid has been estimated from the X-ray diffraction studies and is around 56% with respect to polyaniline emeraldine base. The change in dielectric permittivity with respect to temperature and frequency is explained on the basis of interfacial polarisation. AC conductivity is evaluated from the observed dielectric permittivity. The values of AC and DC conductivity and activation energy are calculated. The activation energy values suggested that the hopping conduction is the prominent conduction mechanism in this system.

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Leachate from an untreated landfill or landfill with damaged liners will cause the pollution of soil and ground water. Here an attempt was made to generate knowledge on concentrations of all relevant pollutants in soil due to municipal solid waste landfill leachate and its migration through soil and also to study the effect of leachate on the engineering properties of soil. To identify the pollutants in soil due to the leachate generated from municipal solid waste landfill site, a case study on an unlined municipal solid waste landfill at Kalamassery has been done. Soil samples as well as water samples were collected from the site and analysed to identify the pollutants and its effect on soil characteristics. The major chemicals in the soil were identified as Ammonia, Chloride, Nitrate, Iron, Nickel, Chromium, Cadmium etc.. Engineering properties of field soil samples show that the chemicals from the leachate of landfill may have effect on the engineering properties of soil. Laboratory experiments were formulated to model the field around an unlined MSW landfill using two different soils subjected to a synthetic leachate. The Maximum change in chemical concentration and engineering property was observed on soil samples at a radial distance of 0.2 m and at a depth of 0.3 m. The pollutant (chemicals) transport pattern through the soil was also studied using synthetic leachate. To establish the effect of pollutants (chemicals) on engineering properties of soil, experiments were conducted on two types soils treated with the synthetic chemicals at four different concentrations. Analyses were conducted after maturing periods of 7, 50, 100 and 150 days. Test soils treated with maximum chemical concentration and matured for 150 days were showing major change in the properties. To visualize the flow of pollutants through soil in a broader sense, the transportation of pollutants through soil was modeled using software ‘Visual MODFLOW’. The actual field data collected for the case study was used to calibrate the modelling and thus simulated the flow pattern of the pollutants through soil around Kalamassery municipal solid waste landfill for an extent of 4 km2. Flow was analysed for a time span of 30 years in which the landfill was closed after 20 years. The concentration of leachate beneath the landfill was observed to be reduced considerably within one year after closure of landfill and within 8 years, it gets lowered to a negligible level. As an environmensstal management measure to control the pollution through leachate, permeable reactive barriers are used as an emerging technology. Here the suitability of locally available materials like coir pith, rice husk and sugar cane bagasse were investigated as reactive media in permeable reactive barrier. The test results illustrates that, among these, coir pith was showing better performance with maximum percentage reduction in concentration of the filtrate. All these three agricultural wastes can be effectively utilized as a reactive material. This research establishes the influence of leachate of municipal solid waste landfill on the engineering properties of soil. The factors such as type of the soil, composition of leachate, infiltration rate, aquifers, ground water table etc., will have a major role on the area of influence zone of the pollutants in a landfill. Software models of the landfill area can be used to predict the extent and the time span of pollution of a landfill, by inputting the accurate field parameters and leachate characteristics. The present study throws light on the role of agro waste materials on the reduction of the pollution in leachate and thus prevents the groundwater and soil from contamination

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Mineral and geochemical investigations were carried out on soil samples and fresh rock (trachytes) from two selected soil profiles (TM profile on leptic aluandic soils and TL profile on thapto aluandic-ferralsols) from Mount Bambouto to better understand geochemical processes and mineral paragenesis involved in the development of soils in this environment. In TM profile, the hydrated halloysites and goethite occur in the weathered saprolite boulders of BC horizon while dehydrated halloysite, gibbsite and goethite dominate the soils matrices of BC and A horizons. In TL profile, the dehydrated halloysites and goethite are the most abundant secondary minerals in the weathered saprolites of C and BC horizons while gibbsite, hematite and kaolinite occur in the soil matrices of BC, B and A horizons. The highest gibbsite content is in the platy nodules of B horizon. In both soil profiles, organo-metal complexes (most likely of AI and Fe) are present in the surface A horizon. Geochemically, between the fresh rock and the weathered saprolites in both soils, SiO2, K2O, CaO, Na2O and MgO contents decrease strongly while Fe2O3 and Al2O3 tend to accumulate. The molar ratio of SiO2/Al2O3 (Ki) and the sum of Ca, Mg, K and Na ions (TRB) also decreases abruptly between fresh rocks and the weathered saprolites, but increases significantly at the soil surface. The TM profile shows intense Al enrichment whereas the TL profile highlights enrichment in both AI and Fe as the weathering progresses upwards. Both soil profiles are enriched in Ni, Cu, Ba and Co and depleted in U, Th, Ta, Hf, Y, Sr, Pb, Zr and Zn relative to fresh rock. They also show a relatively low fractionation of the rare earth elements (REE: La, Nd, Sm, Eu, Tb, Yb and Lu), except for Ce which tends to be enriched in soils compared to CI chondrite. All these results give evidence of intense hydrolysis at soil deep in Mount Bambouto resulting in the formation of halloysite which progressively transforms into gibbsite and/or dehydrated halloysite. At the soil surface, the prominent pedogenetic process refers to andosolization with formation of organo-metal complexes. In TL profile, the presence of kaolinite in soil matrices BC and B horizons is consistent with ferralitization at soil deep. In conclusion, soil forming processes in Mount Bambouto are strongly influenced by local climate: (i) in the upper mountain (>2000 m), the fresh, misty and humid climate favors andosolization; whereas (ii) in the middle lands (1700-2000 m) with a relatively dry climate, both andosolization at the soil surface and ferralitization at soil deep act together. (C) 2009 Elsevier B.V. All rights reserved.

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Gas-phase ozonolysis of alpha-pinene was studied in static chamber experiments under 'OH-free' conditions. A range of multifunctional products-in particular low-volatility carboxylic acids-were identified in the condensed phase using gas chromatography coupled to mass spectrometry after derivatisation. The dependence of product yields on reaction conditions (humidity, choice of OH radical scavengers, added Criegee intermediate scavengers, NO2 etc.) was investigated to probe the mechanisms of formation of these products; additional information was obtained by studying the ozonolysis of an enal and an enone derived from alpha-pinene. On the basis of experimental findings, previously suggested mechanisms were evaluated and detailed gas-phase mechanisms were developed to explain the observed product formation. Atmospheric implications of this work are discussed.

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The alignment of model amyloid peptide YYKLVFFC is investigated in bulk and at a solid surface using a range of spectroscopic methods employing polarized radiation. The peptide is based on a core sequence of the amyloid beta (A beta) peptide, KLVFF. The attached tyrosine and cysteine units are exploited to yield information on alignment and possible formation of disulfide or dityrosine links. Polarized Raman spectroscopy on aligned stalks provides information on tyrosine orientation, which complements data from linear dichroism (LD) on aqueous solutions subjected to shear in a Couette cell. LD provides a detailed picture of alignment of peptide strands and aromatic residues and was also used to probe the kinetics of self-assembly. This suggests initial association of phenylalanine residues, followed by subsequent registry of strands and orientation of tyrosine residues. X-ray diffraction (XRD) data from aligned stalks is used to extract orientational order parameters from the 0.48 nm reflection in the cross-beta pattern, from which an orientational distribution function is obtained. X-ray diffraction on solutions subject to capillary flow confirmed orientation in situ at the level of the cross-beta pattern. The information on fibril and tyrosine orientation from polarized Raman spectroscopy is compared with results from NEXAFS experiments on samples prepared as films on silicon. This indicates fibrils are aligned parallel to the surface, with phenyl ring normals perpendicular to the surface. Possible disulfide bridging leading to peptide dimer formation was excluded by Raman spectroscopy, whereas dityrosine formation was probed by fluorescence experiments and was found not to occur except under alkaline conditions. Congo red binding was found not to influence the cross-beta XRD pattern.

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Alzheimer's disease is more frequent following an ischemic or hypoxic episode, with levels of beta-amyloid peptides elevated in brains from patients. Similar increases are found after experimental ischemia in animals. It is possible that increased beta-amyloid deposition arises from alterations in amyloid precursor protein (APP) metabolism, indeed, we have shown that exposing cells of neuronal origin to chronic hypoxia decreased the secretion of soluble APP (sAPPalpha) derived by action of alpha-secretase on APP, coinciding with a decrease in protein levels of ADAM10, a disintegrin metalloprotease which is thought to be the major alpha-secretase. In the current study, we extended those observations to determine whether the expression of ADAM10 and another putative alpha-secretase, TACE, as well as the beta-secretase, BACE1 were regulated by chronic hypoxia at the level of protein and mRNA. Using Western blotting and RT-PCR, we demonstrate that after 48 h chronic hypoxia, such that sAPPalpha secretion is decreased by over 50%, protein levels of ADAM10 and TACE and by approximately 60% and 40% respectively with no significant decrease in BACE1 levels. In contrast, no change in the expression of the mRNA for these proteins could be detected. Thus, we conclude that under CH the level of the putative alpha-secretases, ADAM10 and TACE are regulated by post-translational mechanisms, most probably proteolysis, rather than at the level of transcription.

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The X-ray diffraction pattern of glassy poly(2-hydroxypropyl ether of bisphenol A) is studied at room temperature on oriented samples in order to associate its different peaks to different structural correlations. On the other hand, X-ray diffraction patterns have been obtained at different temperatures from Tg − 50 K up to Tg + 50 K for the above-mentioned polymer. Attention has been paid to the evolution with temperature of the position of the wide diffraction maximum corresponding to interchain correlations in the polymer. The temperature evolution of this parameter shows a marked discontinuity just at the glass transition temperature.

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Using simultaneous electroencephalography as a measure of ongoing activity and functional magnetic resonance imaging (fMRI) as a measure of the stimulus-driven neural response, we examined whether the amplitude and phase of occipital alpha oscillations at the onset of a brief visual stimulus affects the amplitude of the visually evoked fMRI response. When accounting for intrinsic coupling of alpha amplitude and occipital fMRI signal by modeling and subtracting pseudo-trials, no significant effect of prestimulus alpha amplitude on the evoked fMRI response could be demonstrated. Regarding the effect of alpha phase, we found that stimuli arriving at the peak of the alpha cycle yielded a lower blood oxygenation level-dependent (BOLD) fMRI response in early visual cortex (V1/V2) than stimuli presented at the trough of the cycle. Our results therefore show that phase of occipital alpha oscillations impacts the overall strength of a visually evoked response, as indexed by the BOLD signal. This observation complements existing evidence that alpha oscillations reflect periodic variations in cortical excitability and suggests that the phase of oscillations in postsynaptic potentials can serve as a mechanism of gain control for incoming neural activity. Finally, our findings provide a putative neural basis for observations of alpha phase dependence of visual perceptual performance.

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BACKGROUND: Low vitamin D status has been shown to be a risk factor for several metabolic traits such as obesity, diabetes and cardiovascular disease. The biological actions of 1, 25-dihydroxyvitamin D, are mediated through the vitamin D receptor (VDR), which heterodimerizes with retinoid X receptor, gamma (RXRG). Hence, we examined the potential interactions between the tagging polymorphisms in the VDR (22 tag SNPs) and RXRG (23 tag SNPs) genes on metabolic outcomes such as body mass index, waist circumference, waist-hip ratio (WHR), high- and low-density lipoprotein (LDL) cholesterols, serum triglycerides, systolic and diastolic blood pressures and glycated haemoglobin in the 1958 British Birth Cohort (1958BC, up to n = 5,231). We used Multifactor- dimensionality reduction (MDR) program as a non-parametric test to examine for potential interactions between the VDR and RXRG gene polymorphisms in the 1958BC. We used the data from Northern Finland Birth Cohort 1966 (NFBC66, up to n = 5,316) and Twins UK (up to n = 3,943) to replicate our initial findings from 1958BC. RESULTS: After Bonferroni correction, the joint-likelihood ratio test suggested interactions on serum triglycerides (4 SNP - SNP pairs), LDL cholesterol (2 SNP - SNP pairs) and WHR (1 SNP - SNP pair) in the 1958BC. MDR permutation model testing analysis showed one two-way and one three-way interaction to be statistically significant on serum triglycerides in the 1958BC. In meta-analysis of results from two replication cohorts (NFBC66 and Twins UK, total n = 8,183), none of the interactions remained after correction for multiple testing (Pinteraction >0.17). CONCLUSIONS: Our results did not provide strong evidence for interactions between allelic variations in VDR and RXRG genes on metabolic outcomes; however, further replication studies on large samples are needed to confirm our findings.

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We report the first simultaneous zJHK spectroscopy on the archetypical Seyfert 2 galaxy NGC 1068 covering the wavelength region 0.9-2.4 mu m. The slit, aligned in the north-south direction and centred in the optical nucleus, maps a region 300 pc in radius at subarcsec resolution, with a spectral resolving power of 360 km s-1. This configuration allows us to study the physical properties of the nuclear gas including that of the north side of the ionization cone, map the strong excess of continuum emission in the K band and attributed to dust and study the variations, both in flux and profile, in the emission lines. Our results show the following. (1) Mid- to low-ionization emission lines are split into two components, whose relative strengths vary with the position along the slit and seem to be correlated with the jet. (2) The coronal lines are single-peaked and are detected only in the central few hundred of pc from the nucleus. (3) The absorption lines indicate the presence of intermediate age stellar population, which might be a significant contributor to the continuum in the near-IR spectra. (4) Through some simple photoionization models we find photoionization as the main mechanism powering the emitting gas. (5) Calculations using stellar features point to a mass concentration inside the 100-200 pc of about 1010 M(circle dot).