There are different methods used in the surgical treatment of peripheral nerve injury. In this respect, end-to-end surgical reconnection of the damaged nerve ends or autologous nerve grafts are applied as soon as possible after the injury. When autologous tissue transplant is considered, there are some medical devices available generally for relatively short nerve defects. As a solution for this problem, different tissue engineered nerve conduits have been developed. In the current study, a pHEMA hydrogel membranes were designed to mimic the tubular conduits and they were loaded with 1-6% (w/w) multiwalled carbon nanotubes (mwCNTs) to obtain electrical conductivity. The most important reason for the use of CNTs in peripheral nerve injury is their electrical conductivity. Within the context of the study, the degree of swelling, contact angles, electrical conductivity and mechanical properties of the membranes were analyzed. As the amount of mwCNTs were increased, the contact angles, indicating higher hydrophobicity and the electrical conductivity increased. The tensile test of the mwCNT-pHEMA composite membranes showed that the membranes have viscoelastic structure similar to the structure of the soft tissues. The structure of the mwCNT containing pHEMA composite membranes were analyzed with different microscopical techniques such as SEM, CSLM and microCT. MwCNTs on the hydrogels were morphologically similar to the original. SEM micrographs also showed that the mwCNTs were grouped in clumps on hydrogel surfaces. No mwCNT leaching was observed because the mwCNTs were embedded in the hydrogel, therefore, no cytotoxic effect was observed. The pHEMA hydrogels were porous which is suitable for transportation of materials, electrolytes and gas needed for cell nutrition and growth. In the in vitro studies, SHSY5Y neuroblastoma cells were seeded on the membranes to determine the sustainability and effects of the membranes on the cell growth. Electrical potential of 1 and 2 V were used to stimulate the cells. Microscopical examination with SEM and CSLM, and MTT viability assay were used. The SHSY5Y neuroblastoma cells were attached and proliferated on both the composite and the hydrogel membranes. The cells on pHEMA membranes without mwCNTs, however, were not able to survive after application of electrical potential. As a conclusion, use of composite membranes in the treatment of peripheral nerve injury as a nerve conduit is appropriate. Electrical stimulation, however, did not induce the cells to align in contrast to the expected results, indicating potential and current application regime needs to be optimized to obtain the desired results.

In the present thesis we propose the development of hybrid polymer titanium dioxide (TiO2) nanoparticles for use in biomedical applications. TiO2 exhibits high biocompatibility in the dark however, upon illumination in aqueous media with near UV light it produces an array of reactive oxygen species (ROS) which have the capability to induce death in neighbouring cells. The process of inducing cell death using a photosensitive material which produces ROS is known as photodynamic therapy (PDT) and is used to treat a wide range of maladies from psoriasis to cancer.We have demonstrated the ability to produce anatase nanoparticles with high control over their resulting size through a novel water mediated sol-gel synthetic method in benzyl alcohol, using either Ti(OnPr)4, Ti(OnBu)4 or Ti(OiPr)4 as the metal precursor. Through dynamic light scattering (DLS) analysis we have shown that the mechanism of nanoparticle growth appears to proceed through the agglomeration of primary nanoparticles formed instantly upon adding the reagents together. After synthesis the nanoparticles could be easily redispersed in aqueous media at pH2 with any further agglomeration being controlled by the parent alkoxide.After synthesis the nanoparticles were coated with PEG, conjugated to either a catechol or phosphate as ligand, in order to stabilise the nanoparticles at neutral pH. Uncoated nanoparticles exhibited good photoactive capability in the photooxidation of methylene blue. However, on coating with catechols the photoactivity of the nanoparticles was abolished. Coating with phosph(on)ates on the other hand preserved or even enhanced the photoactivity which makes this system promising for in vivo applications.At the same time this thesis also reports preliminary investigations on the use of TiO2 embedded into the walls of model drug loaded poly electrolyte multilayer microspheres for UV triggered delivery applications.

<p>U prvom delu rada ispitana je adsorpcija četiri grupe organskih&nbsp;jedinjenja: (1) nitroaromatičnih (nitrobenzen), (2) nepolarno alifatičnih&nbsp;(heksan), (3)&nbsp; monoaromatičnih (benzen, toluen, 1,2,3- i 1,2,4-trihlorbenzen) i (4) policikličnih aromatičnih ugljovodonika, PAH&nbsp;(naftalen, fenantren, piren i fluoranten) na vi&scaron;eslojnim ugljeničnim&nbsp;nanocevima (od eng. multiwalled carbon nanotubes, MWCNTs). Cilj&nbsp;ovog dela rada bio je pronaći korelaciju između parametara adsorpcije i&nbsp;fizičko-hemijskih karakteristika organskih molekula, kao i parametara&nbsp;<br />adsorpcije i karakteristika adsorbenata. Na osnovu dobijenih korelacija&nbsp;predložiti mehanizam adsorpcije ispitivanih organskih molekula na&nbsp;MWCNT-u.</p><p>U cilju ispitivanja uticaja kiseoničnih funkcionalnih grupa na povr&scaron;ini&nbsp;MWCNT-a odabrane su tri vrste MWCNT-a: originalni, nemodifikovani&nbsp;MWCNT (OMWCNT) i dve vrste funkcionalno modifikovanog&nbsp;MWCNT-a koji su dobijeni tretiranjem sa kiselinom tokom 3 h&nbsp;(FMWCNT3h) i 6 h (FMWCNT6h). Sve adsorpcione izoterme opisane&nbsp;<br />su Freundlich-ovim modelom. Nelinearnost izotermi bila je u opsegu od&nbsp;0,418 do 0,897. Rezultati pokazuju da dobijeni afiniteti adsorpcije (za ravnotežnu koncentraciju 50% rastvorljivosti jedinjenja u vodi, K_d0,5 S_W) za PAH-ove rastu sa povećanjem specifične povr&scaron;ine (SP) adsorbenta. Veći afiniteti adsorpcije dobijeni su za velike molekule kao &scaron;to su PAH-ovi u poređenju sa malim molekulima (benzen, toluen i heksan) &scaron;to može biti posledica veće kontaktne povr&scaron;ine između većih molekula i povr&scaron;ine adsorbenta. Pozitivna korelacija između afiniteta adsorpcije i hidrofobnosti molekula ukazuje da hidrofobne interakcije dominantno kontroli&scaron;u adsorpciju ispitivanih organskih jedinjenja, osim u slučaju nitobenzena. Da bi se ispitao uticaj &pi;-&pi; interakcija,&nbsp; K_d za odabranu ravnotežnu koncentraciju su normalizovane sa hidrofobno&scaron;ću molekula pri čemu su dobijeni odgovarajući&nbsp; K_d/K_OW&nbsp;odnosi. Za sva ispitivana jedinjenja K_d/K_OW<font size="1">&nbsp;</font>odnosi na svim ispitivanim MWCNT rastu u sledećem nizu: nepolarni alifatični &lt; monoaromatični &lt; PAH-ovi &lt; nitrobenzen, &scaron;to ukazuje da &pi;-&pi; interakcije značajno pobolj&scaron;avaju adsorpciju aromatičnih jedinjenja na MWCNT-u. Snažne interakcije između MWCNT-a i nitrobenzena posledica su formiranja &pi;-&pi; elektron donorsko-akceptorskih (EDA) interakcija izemđu nitroaromatičnih molekula (elektron akceptori)i visoko polarizovane ugljenične povr&scaron;ine nanocevi (elektron donori). Na osnovu dobijenih rezultata može se uočiti da se pri adsorpciji ispitivanihorganskih molekula na MWCNT-u istovreme odigrava vi&scaron;e mehanizama.</p><p>U drugom delu rada ispitan je uticaj ugljeničnog nanomaterijala (od eng.&nbsp;carbon based nanomaterial, CNM) natransport odabranih organskih&nbsp;jedinjenja (1,2,3- i 1,2,4-trihlorbenzena, naftalena, fenantrena, pirena i&nbsp;fluorantena) kroz sediment Dunava. Cilj ovog dela rada bio je ispitati&nbsp;mehanizam transporta odabranih organskih jedinjenja u prisustvu i&nbsp;odsustvu CNM. C/C_0&nbsp;vrednosti, dobijene za vreme trajanja eksperimenta&nbsp;<br />(t=96 h), ispitivanog jedinjenja u eluatu kolone napunjene samo&nbsp;sedimentom rastu u sledećem nizu: fluoranten &lt; piren &lt; fenantren &lt;&nbsp;1,2,4-trihlorbenzen &lt; 1,2,3-trihlorbenzen &lt; naftalen. U cilju ispitivanja&nbsp;uticaja hidrofobnosti ispitivanih molekula na sorpciju u neravnotežnim&nbsp;uslovima, dobijene vrednosti C/C₀ ispitivanih molekula su korelirane sa&nbsp;hidrofobno&scaron;ću molekula. Uočena je negativna korelacija &scaron;to ukazuje da&nbsp;hidrofobniji molekuli pokazuju duže vreme zadržavanja na koloni, a time&nbsp;i veću neravnotežnu sorpcijutokom transporta.&nbsp;</p><p>U prisustvu FMWCNT3h u koloni kojaje napunjena sedimentom može&nbsp;se uočiti da su koncentracije ispitivanih jedinjenja u eluatu manje za 2-3&nbsp;puta. Pri datim uslovima procenat detektovane koncentracije ispitivanog&nbsp;jedinjenja u eluatu raste u sledećem nizu: fluoranten &lt; fenantren &lt; piren &lt; naftalen &lt; 1,2,4-trihlorbenzena &lt; 1,2,3-trihlorbenzen. Predloženi mehanizam je sledeći: na eksperimentalnoj pH (pH=6,5) karboksilne grupe na FMWCNT3h su negativno naelekrisane, s druge strane tačka nultog naelektrisanja sedimenta Dunav je 4, &scaron;to ukazuje da je ukupna povr&scaron;ina pri pH=6,5 negativno naelektrisana. Međutim, metalni oksidi i hidroksidi gvožđa, aluminijuma i nikla na povr&scaron;ini sedimenta uzrokuju pozitivno naelektrisane centre &scaron;to dovodi do depozicije FMWCNT3h kao posledica elektrostatičkog privlačenja. Pri transportu organskih jedinjenja kroz sediment Dunava u prisustvu FMWCNT3h dolazi do simultane sorpcije organskih jedinjenja na organskom ugljeniku sedimenta i do adsorpcije na FMWCNT3h. Kada se pH vrednost poveća smanjuje se pozitivno naelekrisanje metalnih&nbsp; oksida i hidroksida na povr&scaron;ini sedimenta &scaron;to dovodi do povećane mobilnosti FMWCNT3h, a time i organskih jedinjenja adsorbovanih na njima. Svi rezultati ukazuju da pH vrednost ima veoma značajnu ulogu i može povećati &nbsp;transport funkcionalizovanog MWCNT-a, a time i transport organskih molekula adsorbovanih na njima.</p> / <p>The first part of the thesis investigates the adsorption of four&nbsp;groups of organic compounds (OCs): (1) nitroaromatics (nitrobenzene),&nbsp;(2) nonpolar aliphatics (hexane), (3) monoaromatics (benzene, toluene,&nbsp;1,2,3- and 1,2,4-trichlorobenzene) and (4) polycyclic aromatic&nbsp;hydrocarbons (PAHs, napthalene,&nbsp; phenanthrene, pyrene and&nbsp;fluoranthene) on multiwalled carbon nanotubes (MWCNTs). This part of&nbsp;the work aimed to find a correlationbetween the adsorption parameters&nbsp;and physical-chemical properties of the organic molecules, as well as the&nbsp;parameters of adsorption and the characteristics of the adsorbents. On the&nbsp;basis of the obtained correlations the adsorption mechanism was&nbsp;proposed. In order to investigate the influence which oxygen containing&nbsp;functional groups exert on the adsorption process, three MWCNTs were&nbsp;used: the pristine (original, as-received) MWCNTs (OMWCNT) and two&nbsp;<br />MWCNTs functionally modified by acid treatment of OMWCNT over 3&nbsp;h and 6 h (FMWCNT3h, FMWCNT6h). All adsorption isotherms well&nbsp;fitted with the Freundlich model. The nonlinearity of the isotherms&nbsp;ranged from 0.418 to 0.897. The results show that K_d&nbsp;values for PAHs&nbsp;increased with increasing specific surface areas (SSAs). The adsorption&nbsp;affinities of the larger molecular size OCs (PAHs) were higher &nbsp;than those of the smaller size OCs (benzene, toluene and hexane) which is probably due to their large contact area with the surface of the adsorbent. Adsorption of OCs on MWCNTs was mainly controlled by hydrophobic interactions, except for the nitroaromatic compound, as shown by the increasing adsorption affinities with the compound&rsquo;s hydrophobicity. K_OW-normalized adsorption coefficients (K_d/K_OW) for all the investigated compounds on all the MWCNTs followed the order: nonpolar aliphatic &lt; monoaromatics &lt; PAHs &lt; nitroaromatic, implying that &pi;-&pi; interactions enhanced the adsorption of aromatics on the MWCNTs. It can be concluded that the strong adsorptiveinteractions between the MWCNTs and nitroaromatics was due to the &pi;-&pi; electron-donor&ndash;acceptor (EDA) interaction between nitroaromatic molecules (electron acceptors) and the highly polarisable graphene sheets(electron donors) of the carbon nanotubes. Based on the obtained results, it can be concluded that multiple mechanisms control the adsorption of organic compounds on MWCNTs.</p><p>In the second part, the influence of carbon based nanomaterials CNM on&nbsp;transport of selected organic compounds (1,2,3 - and 1,2,4-trichlorobenzene, naphthalene, phenanthrene, pyrene and fluoranthene)&nbsp;through sediment Danube was investigated. &nbsp;The aim of this part of the&nbsp;work was to investigate the transport mechanism of selected organic&nbsp;compounds in the presence and absence of CNM. The C/C_0&nbsp;values for the&nbsp;tested compounds in the eluate of the column filled with sediment only&nbsp;increased in the following order: fluoranthene &lt;pyrene &lt;phenanthrene&nbsp;&lt;1,2,4-trichlorobenzene &lt;1,2,3-trichlorobenzene &lt;naphthalene. In order&nbsp;to investigate the influence of&nbsp; hydrophobicity of the investigated&nbsp;compounds on the nonequilibrium sorption, the obtained C/C_0&nbsp;values (for&nbsp;the duration of the experiment, t = 96 h) for these molecules were&nbsp;correlated with the hydrophobicity of the molecules. There was a&nbsp;negative correlation, indicating that more hydrophobic molecules show&nbsp;long residence times in the column, and thus had higher non-equilibrium&nbsp;sorption during transport. In the presence of FMWCNT3h in the column&nbsp;filled with sediment, it can be observed that the concentrations of&nbsp;compounds in the column eluate decreased by factors of 2-3. C/C_0&nbsp;values&nbsp;for the investigated compounds in the eluate increased in the following&nbsp;order: fluoranthene &lt;phenanthrene &lt;pyrene &lt;naphthalene &lt;1,2,4-trichlorobenzene &lt;1,2,3-trichlorobenzene. The proposed mechanism is as&nbsp;follows: under the experimental pH (pH = 6.5), carboxyl groups are&nbsp;negatively charged on the surface of FMWCNT3h and the point of zero&nbsp;charge of the Danube sediment is 4, which indicates thatthe total surface of the Danube sediment at pH 6.5 isnegatively charged. However, metal oxides and hydroxides of iron, aluminum and nickel on the surface of the sediment cause a positively charged centre that leads to the deposition of FMWCNT3h as a result of electrostatic attraction. Transport of organic compounds through the Danube sediment in the presence FMWCNT3h leads to the simultaneous &nbsp;sorption oforganic compounds on the sediment organic carbon and the adsorption of &nbsp;FMWCNT3h. When the pH increased, the positive charge of metal oxides and hydroxides on the sediment surface decreased, which leads to increased FMWCNT3h mobility and thus the organic compounds adsorbed on them. All results indicate that the pH value plays animportant role and can increase the transport of functionally modified MWCNT&#39;s, and thus the transport of organic molecules adsorbed on them.&nbsp;</p>

In recent years, respiratory diseases have emerged as a leading cause of mortality across the globe. In the United States alone respiratory diseases are the fourth leading cause of deaths annually. Moreover, with the rapid increase of industrialization and urbanization, the occurrences of respiratory diseases are expected to remain high with strong chances of increasing in the future. To ameliorate the epidemic of respiratory disease, it is first important to understand its underlying mechanisms. Respiratory research studies in animals have elucidated the chronological order of the pathological events and systemic responses inside the lung, but understanding the response of individual cell types inside the lung is necessary to outline the initiators and mediators of the pathological events. Many research studies have aimed to understand the behavior of individual cell types, from the lung, under different pathological conditions specific to the respiratory system. However, the cell culture systems used in most of these studies were limited by the absence of the dynamic cell growth environment present in actual lung tissues. The lung exists in a mechanically active environment, where different amounts of circumferential and longitudinal expansion and contraction occur during breathing movements. Thus, simulating the biomechanical environment in in vitro cell culture models may improve the cellular functionality and the outcome of the research studies. Moreover, the stimulation of biomechanical forces in in vitro cell cultures provides the advantage of mimicking the mechanical environment, related to different pathological conditions. In our study we used a dynamic in vitro cell culture system capable of implementing cyclic equibiaxial deformation in cell monolayers to stimulate different biomechanical environments similar to conditions inside the lung. The dynamic cell growth condition was used to determine the effects of ventilator-induced lung injury and nano-material/pollutant exposure in A549 cell cultures. Examples of such pollutants are diesel particulate matter, multi-walled carbon nanotubes, and single-walled carbon nanotubes. Our results indicated that the dynamic cell growth condition specific to ventilator induced lung injury facilitated an increase in inflammatory and tissue remodeling activities in A549 cells. Under the nano-material/pollutant exposure assessment studies, the dynamic cell growth condition induced changes in inflammation and oxidative stress level which closely resembled those in in vivo studies.

No description available.

PTMO-urethane and urea diacrylates (UtDA, UrDA) were synthesized from a two-step reactions of bis (4-isocyanatocyclohexyl) methane (HMDI) with either α,Ï -hydroxy-terminated poly (tetramethylene oxide) (PTMO Mn 250, 1000, 2000 and 2900 g/mol) or α,Ï -aminopropyl-terminated PTMO and 2-hydroxyethyl acrylate (HEA). PTMO-based ester precursors (EtDA) were also synthesized from α,Ï -hydroxy-terminated PTMO (Mn 1000 and 2000 g/mol). Two bis acetoacetates were synthesized from acetoacetylation of 1,4-butanediol and 250 g/mol hydroxy-terminated PTMO with tert-butyl acetoacetate. ¹H NMR spectroscopy confirmed the structure and average molecular weights (Mn)of diacrylates. Mn of these precursors were in the range of 950 to 3670 g/mol by ¹H NMR. The rheological properties of diacrylates were studied and activation energies for flow were calculated. Activation energies increased with increasing Mn and hydrogen-bond segment content. Michael carbon addition was employed to covalently crosslink the precursors resulting in networks with gel fractions better than 90%. DSC and DMA experiments revealed that networks had a broad distribution of glass transition temperatures depending on Mn and degree of hydrogen bonding present in the diacrylates. Their Tg's varied from -61 ºC to 63 ºC depending on the crosslinking density and hydrogen-bonding segment content. TGA revealed that UtDA and UrDA networks had an improved thermal stability compared to their EtDA counterparts. Tensile properties showed a variation depending on the structure and Mn of diacrylate and BisAcAc precursors. The storage moduli of networks precursor change from 25.3 MPa to 2.0 MPa with increasing Mn of the urethane diacrylate Elongation at break increased from 255% to 755 % for the same networks. The Young's moduli increased from 3.27 MPa for EtDA 2000 to 311.1 MPa for UrDA 2000 which was attributed to increasing degree of hydrogen-bonding. Acid functionalization of C70 P Baytubes multiwalled carbon nanotubes (MWCNT) generated acid-functionalized nanotubes (MWCNT-COOH). Suspension of MWCNT-COOH in organic solvents (chloroform, toluene, THF, DMF and 2-propanol) were prepared. DLS indicated average particle diameters of MWCNT-COOH in DMF and in 2-propanol were 139 nm and 162 nm respectively. FESEM of suspensions revealed aggregate free dispersion of MWCNT-COOH in DMF and 2-propanol. MWCNT-COOH containing composite networks were prepared. FESEM images of fracture surfaces of UtDA showed MWCNT-COOH were well-dispersed in the composites. DMA showed an increase in the rubbery plateau modulus which correlated with the MWCNT-COOH content in the networks. Tensile testing also revealed a relationship between MWCNT-COOH content and young's moduli and strain at break of networks. Storage moduli of networks increased from 25 MPa to 211 MPa with increasing MWCNT-COOH content whereas elongation at break decreased from 255 % to 146 %. UtDAs and pentaerythritol tetraacrylate (PETA) were crosslinked under UV radiation (6 passes, 1.42 ± 0.05 W.cm2 for each pass) in the presence of 2,2-dimethoxy-2-phenylacetophenone (DMPA) (1 wt. % of the mixture) UV initiator. DMA demonstrated the presence of broad glass transition regions with a range of Tg's which varied from -60 °C to -30°C. Tensile testing also revealed the relationship between Young's moduli, strain at break and the molecular weight of the diacrylates. The increasing molecular weight of urethane diacrylate precursors caused a drop in the storage moduli of networks from 15.8 MPa to 1.4 MPa and an increase in elongation at break from 76 % to 132 %. / Master of Science

La microscopie à force atomique exploite les interactions entre une sonde et un échantillon. Les nanotubes de carbone représentent la sonde idéale, ils sont: fins, robustes, peu réactifs et ont un haut rapport d'aspect. L'utilisation à grande échelle des sondes à nanotubes de carbone passe par l'étude de leur comportement mécanique en contact avec une surface. Nous étudions deux types de sondes: les sondes avec nanotubes multiparois et les sondes avec nanotubes monoparois. Pour les nanotubes multiparois nous avons utilisé trois mode de fonctionnement AFM différents que sont les modes contact, modulation de fréquence et bruit thermique. Les résultats expérimentaux sont comparés à des modèles mécaniques que nous avons développés. Les études des nanotubes monoparois ont été réalisées à partir d'un AFM interférométrique. Ces mesures nous ont permis de déterminer l'énergie d'adhésion par unité de longueur d'un nanotube monoparoi sur des surfaces de graphite et mica.Enfin nous présentons deux applications des sondes AFM avec nanotube multiparoi. La première est un projet de sondes électrochimiques pour lesquelles un nanotube multiparoi sert de nanolocalisateur. La seconde est une étude par AFM d'une interface air-liquide de fluides complexes. / Atomic force microscopy exploits interactions between a probe and a sample. Carbon nanotubes represent the ideal probe; they are thin with a high aspect ratio, robustes and few reactive. The widespread use of carbon nanotube probes needs the study of their mechanical behavior in contact with a surface. We study two types of probes: probes with multiwalled nanotubes and probes with singlewalled nanotubes. For multiwalled nanotubes, we used three differents AFM modes that are contact, frequency modulation and thermalnoise. The experimental results are compared with mechanical models that we developed. Studies of singlewalled nanotubes have been produced from an interferometric AFM. These measures have enabled us to determine the adhesion energy per unit length of singlewalled nanotubes on graphite and mica surfaces.Finally we present two applications of AFM probes with multiwall nanotubes. The first is a project of electrochemical sensors for which a multiwall nanotube is used as a nanolocalisator. The second is a study by AFM of air-liquid interface of complex fluids.

Neste trabalho são apresentados resultados sobre o desenvolvimento de um sensor visando à utilização no monitoramento de peróxido de hidrogênio em amostras de reações Fenton. Superfícies eletródicas modificadas com filmes de poli-azul de metileno (PMB) e óxido de rutênio de hexacianoferrato (RuOHCF) sem e com a incorporação de nanotubos de carbono de paredes múltiplas (MWCNTs) foram utilizadas para a detecção amperométrica de peróxido de hidrogênio. O efeito da ordem de deposição do PMB e MWCNT foi avaliado por voltametria cíclica e espectroscopia de impedância eletroquímica. Estudos realizados por voltametria cíclica indicaram que a superfície modificada com PBM/MWCNTs facilita a redução catódica do peróxido de hidrogênio, processo que ocorre em 0,0 V vs. Ag/AgCl/KCl(sat). O método para a detecção de peróxido de hidrogênio apresentou uma resposta linear de 109 a 3000 &#181;mol L-1, com limite de detecção de 20,7 &#181;mol L-1 e sensibilidade de 108 &#181;A mmol-1 L cm-2. O eletrodo modificado com RuOHCF foi utilizado para a detecção amperométrica de peróxido de hidrogênio por análise em injeção em fluxo (FIA). O método apresentou uma resposta linear de 10 a 5000 &#181;mol L-1 e limite de detecção de 1,7 &#181;mol L-1. Aplicações em amostras comerciais também foram realizadas, e os resultados foram concordantes com os obtidos por método padrão. Estudos sobre o processo eletrocatalítico da reação de peróxido de hidrogênio em filmes de RuOHCF foram investigados utilizando eletrodo rotativo. A incorporação de MWCNTs na superfície eletródica também foi analisada com o filme de RuOHCF. Os resultados indicaram que a presença de MWCNTs melhorou a resposta do sensor para peróxido de hidrogênio em potenciais próximos a 0,0 V vs. Ag/AgCl/KCl(sat). A influência da quantidade de MWCNTs foi avaliada por amperometria em 0,0 V vs. Ag/AgCl/KCl(sat) na presença de peróxido de hidrogênio. O eletrodo modificado com 100 &#181;g de MWCNTs e posterior deposição do filme de RuOHCF apresentou melhores características analíticas. Obteve-se como resultado uma curva analítica em um intervalo de 0,1 a 10 mmol L-1, originando uma reta de acordo com a equação: -I (&#181;A) = 0,26 + 31,2 [H2O2] (mmol L-1), R2= 0,9999. A sensibilidade foi de 1560 &#181;A mmol-1 L cm-2 e os limites de detecção e quantificação foram estimados em 4,7 (S/N = 3) e 15,8 (S/N = 10) &#181;mol L-1, respectivamente. Comparando-se as características analíticas dos filmes de PMB e RuOHCF depositados na superfície dos MWCNTs, aquele que apresentou melhor resultado foi o eletrodo modificado com MWCNTs e RuOHCF por ter melhor limite de detecção e maior sensibilidade. Esse eletrodo modificado com MWCNTs e RuOHCF foi utilizado para monitorar o consumo de peróxido de hidrogênio em amostras de reação Fenton. Também foi avaliado o efeito da presença de Fe3+ contido no próprio processo de degradação. A interferência foi eliminada complexando o Fe3+ com oxalato. Finalmente, o eletrodo foi utilizado para monitorar a concentração de peróxido de hidrogênio na degradação de fenol e os resultados foram concordantes com os obtidos por método espectrofotométrico / This work presents results on the development of a sensor to monitor the hydrogen peroxide content in samples of Fenton reaction. The electrode surface was modified with films of poly-methylene blue (PMB) and ruthenium oxide hexacyanoferrate (RuOHCF). In some cases, multiwalled carbon nanotubes (MWCNT) were also used. The effect of the order of deposition of PMB and MWCNTs was evaluated by cyclic voltammetry and electrochemical impedance spectroscopy. The influence of immobilization of various platforms in the performance of fabricated sensors for hydrogen peroxide was also studied. Cyclic voltammetry experiments indicated that the surface modified with PMB/MWCNTs facilitates the cathodic reduction of hydrogen peroxide, a process that occurred at 0.0 V vs. Ag/AgCl/KCl(sat). The method showed a linear response from 109 to 3000 &#181;mol L-1 hydrogen peroxide. The limit of detection was estimated as 20.7 (S/N = 3) &#181;mol L-1 with a sensitivity of 108 &#181;A mmol-1 L cm-2. Electrodes modified with RuOHCF films were used for the amperometric detection of hydrogen peroxide by flow injection analysis (FIA).The method showed a linear response from 10 to 5000 &#181;mol L-1 and a detection limit of 1.7 &#181; mol L-1. Analyses of hydrogen peroxide in commercial samples were also performed, and the results agreed with those obtained by a standard method. Studies on the kinetics of the electrocatalytic reduction of hydrogen peroxide in RuOHCF films were carried out using rotating disc voltammetric. The immobilization of MWCNTs on RuOHCF films was also investigated. The results indicated that the presence of MWCNTs facilitated the electrocatalytic reduction of hydrogen peroxide at potential values near to 0.0 V vs. vs. Ag/AgCl/KCl(sat). The influence of the amount of MWCNTs was studied by amperometry at 0.0 V vs. vs. Ag/AgCl/KCl(sat) in the presence of hydrogen peroxide. The electrode modified with 100 &#181;g of MWCNTs and subsequent deposition of the RuOHCF film showed better analytical characteristics. An analytical curve ranging from 0.1 to 10 mmol L-1 hydrogen peroxide was obtained, resulting in a straight line according to the equation: -I (&#181;A) = 0.26 + 31.2 [H2O2] (mmol L-1), R2= 0.9999. The sensitivity was found to be 1560 &#181;A mmol-1 L cm-2 and the detection and quantification limits were estimated at 4.7 (S / N = 3) and 15.8 (S / N = 10) mmol L-1, respectively. Electrodes modified with MWCNTs and RuOHCF films leaded to better detection limit and sensitivity in comparison to those modified with MWCNTs and PMB. This MWCNTs and RuOHCF modified electrode was used to monitor the consumption of hydrogen peroxide in samples of Fenton reaction and the effect of Fe3+ generated in the degradation process was also examined. The interference was minimized by adding oxalate to the samples. Finally, the sensor was used to monitor the concentration of hydrogen peroxide in the degradation of phenol and the results were in agreement with those obtained by using spectrophotometry

Neste trabalho são apresentados resultados sobre o desenvolvimento de um sensor visando à utilização no monitoramento de peróxido de hidrogênio em amostras de reações Fenton. Superfícies eletródicas modificadas com filmes de poli-azul de metileno (PMB) e óxido de rutênio de hexacianoferrato (RuOHCF) sem e com a incorporação de nanotubos de carbono de paredes múltiplas (MWCNTs) foram utilizadas para a detecção amperométrica de peróxido de hidrogênio. O efeito da ordem de deposição do PMB e MWCNT foi avaliado por voltametria cíclica e espectroscopia de impedância eletroquímica. Estudos realizados por voltametria cíclica indicaram que a superfície modificada com PBM/MWCNTs facilita a redução catódica do peróxido de hidrogênio, processo que ocorre em 0,0 V vs. Ag/AgCl/KCl(sat). O método para a detecção de peróxido de hidrogênio apresentou uma resposta linear de 109 a 3000 &#181;mol L-1, com limite de detecção de 20,7 &#181;mol L-1 e sensibilidade de 108 &#181;A mmol-1 L cm-2. O eletrodo modificado com RuOHCF foi utilizado para a detecção amperométrica de peróxido de hidrogênio por análise em injeção em fluxo (FIA). O método apresentou uma resposta linear de 10 a 5000 &#181;mol L-1 e limite de detecção de 1,7 &#181;mol L-1. Aplicações em amostras comerciais também foram realizadas, e os resultados foram concordantes com os obtidos por método padrão. Estudos sobre o processo eletrocatalítico da reação de peróxido de hidrogênio em filmes de RuOHCF foram investigados utilizando eletrodo rotativo. A incorporação de MWCNTs na superfície eletródica também foi analisada com o filme de RuOHCF. Os resultados indicaram que a presença de MWCNTs melhorou a resposta do sensor para peróxido de hidrogênio em potenciais próximos a 0,0 V vs. Ag/AgCl/KCl(sat). A influência da quantidade de MWCNTs foi avaliada por amperometria em 0,0 V vs. Ag/AgCl/KCl(sat) na presença de peróxido de hidrogênio. O eletrodo modificado com 100 &#181;g de MWCNTs e posterior deposição do filme de RuOHCF apresentou melhores características analíticas. Obteve-se como resultado uma curva analítica em um intervalo de 0,1 a 10 mmol L-1, originando uma reta de acordo com a equação: -I (&#181;A) = 0,26 + 31,2 [H2O2] (mmol L-1), R2= 0,9999. A sensibilidade foi de 1560 &#181;A mmol-1 L cm-2 e os limites de detecção e quantificação foram estimados em 4,7 (S/N = 3) e 15,8 (S/N = 10) &#181;mol L-1, respectivamente. Comparando-se as características analíticas dos filmes de PMB e RuOHCF depositados na superfície dos MWCNTs, aquele que apresentou melhor resultado foi o eletrodo modificado com MWCNTs e RuOHCF por ter melhor limite de detecção e maior sensibilidade. Esse eletrodo modificado com MWCNTs e RuOHCF foi utilizado para monitorar o consumo de peróxido de hidrogênio em amostras de reação Fenton. Também foi avaliado o efeito da presença de Fe3+ contido no próprio processo de degradação. A interferência foi eliminada complexando o Fe3+ com oxalato. Finalmente, o eletrodo foi utilizado para monitorar a concentração de peróxido de hidrogênio na degradação de fenol e os resultados foram concordantes com os obtidos por método espectrofotométrico / This work presents results on the development of a sensor to monitor the hydrogen peroxide content in samples of Fenton reaction. The electrode surface was modified with films of poly-methylene blue (PMB) and ruthenium oxide hexacyanoferrate (RuOHCF). In some cases, multiwalled carbon nanotubes (MWCNT) were also used. The effect of the order of deposition of PMB and MWCNTs was evaluated by cyclic voltammetry and electrochemical impedance spectroscopy. The influence of immobilization of various platforms in the performance of fabricated sensors for hydrogen peroxide was also studied. Cyclic voltammetry experiments indicated that the surface modified with PMB/MWCNTs facilitates the cathodic reduction of hydrogen peroxide, a process that occurred at 0.0 V vs. Ag/AgCl/KCl(sat). The method showed a linear response from 109 to 3000 &#181;mol L-1 hydrogen peroxide. The limit of detection was estimated as 20.7 (S/N = 3) &#181;mol L-1 with a sensitivity of 108 &#181;A mmol-1 L cm-2. Electrodes modified with RuOHCF films were used for the amperometric detection of hydrogen peroxide by flow injection analysis (FIA).The method showed a linear response from 10 to 5000 &#181;mol L-1 and a detection limit of 1.7 &#181; mol L-1. Analyses of hydrogen peroxide in commercial samples were also performed, and the results agreed with those obtained by a standard method. Studies on the kinetics of the electrocatalytic reduction of hydrogen peroxide in RuOHCF films were carried out using rotating disc voltammetric. The immobilization of MWCNTs on RuOHCF films was also investigated. The results indicated that the presence of MWCNTs facilitated the electrocatalytic reduction of hydrogen peroxide at potential values near to 0.0 V vs. vs. Ag/AgCl/KCl(sat). The influence of the amount of MWCNTs was studied by amperometry at 0.0 V vs. vs. Ag/AgCl/KCl(sat) in the presence of hydrogen peroxide. The electrode modified with 100 &#181;g of MWCNTs and subsequent deposition of the RuOHCF film showed better analytical characteristics. An analytical curve ranging from 0.1 to 10 mmol L-1 hydrogen peroxide was obtained, resulting in a straight line according to the equation: -I (&#181;A) = 0.26 + 31.2 [H2O2] (mmol L-1), R2= 0.9999. The sensitivity was found to be 1560 &#181;A mmol-1 L cm-2 and the detection and quantification limits were estimated at 4.7 (S / N = 3) and 15.8 (S / N = 10) mmol L-1, respectively. Electrodes modified with MWCNTs and RuOHCF films leaded to better detection limit and sensitivity in comparison to those modified with MWCNTs and PMB. This MWCNTs and RuOHCF modified electrode was used to monitor the consumption of hydrogen peroxide in samples of Fenton reaction and the effect of Fe3+ generated in the degradation process was also examined. The interference was minimized by adding oxalate to the samples. Finally, the sensor was used to monitor the concentration of hydrogen peroxide in the degradation of phenol and the results were in agreement with those obtained by using spectrophotometry

The thesis relates to synthesis and investigation of nanostructured polymer composites based on oligomers of cyanate esters of bisphenol a (DCBA) or cyclic butylene terephthalate (CBT) and multiwalled carbon nanotubes (MWCNTS). Catalytic effect of mwcnts in process of DCBA polycyclotrimerization as well as in cbt polymerization has been observed. Significant increase in crystallization temperature of nanocomposites based on polybutylene terephthalate (cPBT) with adding of MWCNTS is observed. The effect of processing method of cpbt/mwcnts nanocomposites on its electrical properties has been found. It has been established that the additional heating of the samples (annealing) at temperatures above melting of cPBT leads to reagglomeration of MWCNTS in the system. It is established that reagglomeration of MWCNTS results in increase of conductivity values of nanocomposites due to formation of percolation pathways of MWCNTS through polymer matrix. In the case of polycyanurate matrix (PCN), it is found that addition of small mwcnts contents (0.03-0.06 weight percents) provides increasing tensile strength by 62-94 percents. It has been found that addition of even 0.01 weight percents of MWCNTS provides significant increase in storage modulus of cPBT matrix. This is explained by effective dispersing of small amount of the nanofiller during in situ synthesis of pcn or cpbt matrix that is confirmed by microscopy techniques. It has been established that the properties of the nanocomposites based on heterocyclic esters and MWCNTS can be varied from isolator to conductor and has low percolation thresholds (0.22 and 0.38 weight percents for cPBT and PCN nanocomposites respectively). The conductivity of samples is particularly stable on a very large range of temperature from 300 to 10 degrees Kelvin that make these materials perspective for practical applications in microelectronics, as parts of aircraft and space constructions.