Letteratura scientifica selezionata sul tema "Carbon"

The rapid and steady increase in the concentration of CO2, the most abundant greenhouse gas in the atmosphere, leads to extreme weather and climate events. Due to the burning of fossil fuels (oil, coal and natural gas), the concentration of CO2 in the air has been increasing in recent decades by more than 2 ppm per year, and in the last year alone - by 3.29 ppm. To prevent the "worst" scenarios of climate change, immediate and significant reductions in CO2 emissions through carbon management are needed. Aim. Analysis of the current state of research and prospects for the use of carbonic anhydrase in environmental decarbonization programs. Results. Carbonic anhydrase (CA) is an enzyme that accelerates the exchange of CO2 and HCO3 in solution by a factor of 104 to 106. To date, 7 types of CAs have been identified in different organisms. CA is required to provide a rapid supply of CO2 and HCO3 for various metabolic pathways in the body, explaining its multiple independent origins during evolution. Enzymes isolated from bacteria and mammalian tissues have been tested in CO2 sequestration projects using carbonic anhydrase (CA). The most studied is one of the isoforms of human KAz - hCAII - the most active natural enzyme. Its drawbacks have been instability over time, high sensitivity to temperature, low tolerance to contaminants such as sulphur compounds and the impossibility of reuse. Molecular modelling and enzyme immobilisation methods were used to overcome these limitations. Immobilisation was shown to provide greater thermal and storage stability and increased reusability. Conclusions. Capturing carbon dioxide using carbonic anhydrase (CA) is one of the most cost-effective methods to mitigate global warming, the development of which requires significant efforts to improve the stability and thermal stability of CAs.

This research is conducted to produce carbons from coconut fibre which approach to activated carbon clause continue with carbon surface modification and the adsorption examination to Cu(II) ions. The research consist of several phase. Carbon making of coconut fibre conducted by carbonization processes at 320-400oC with temperature interval 20oC. Carbon yielded in characterized moisture content, ash content and its adsoprtion to iodium. The carbon surface modification conducted by loaded 2-mercaptobenzotiazol (MBT) on carbon. The adsorpsibility of carbon-MBT tested by influence of contact time, pH, and the isoterm adsorption pattern. The result of the study showed carbonization of coconut fibre which approach the requirement of SII No.0258-89 gained at temperature 320oC. In the present study equilibrium time of 10 minute and pH was found to be optimum for both adsorbent. While type of isothermal adsorption from carban and carbon-MBT adsorbent followed the Langmuir adsorption pattern.

Acetylene (C2H2) was used as carbon source gas, nitrogen (N2) as dilution gas. The electric properties of carbon fibers was briefly discussed by energizing the carbon fibers in vacuum condition which were applied for the preparation of carbon/carbon composites by the method of chemical vapor deposition. The deposition mechanism and microstructure of pyrolytic carbons in carbon fibers under different deposition crafts were also discussed. Results indicate that the greater the initial voltage, the higher the temperature, we can change the deposition temperature by changing the initial voltage according to the relationship between the brightness and the surface temperature of carbon fibers. The surface of carbon fibers will be etched in the process of electrifying which would make the pyrolytic carbons preferred deposition on the etching point which became the growth center in the early deposition process. The pyrolytic carbons deposited with a spherical microcrystalline structure under the gas flow of C3H6/N2=2:3, When the rate of gas flow is C3H6/N2=1:2, The pyrolytic carbons deposited with a spherical microcrystalline structure after deposited for 0.5h, but after deposited for 1h, the deposition of large patches of molecular is dominant which lead to that: from a macro perspective, the pyrolytic carbons were a layered structure, From a microscopic perspective, they were a spherical microcrystalline structure with different size.

A research on the preparation of Carbon Waste Powder, CWP, was conducted and made from carbon rod waste which was extracted from used zinc-carbon batteries. This research was an effort to overcome environmental problem caused by battery waste by converting into adsorbent for methyl orange (MO) that frequently used by textile industries. The prepared powder was then analyzed to understand its characteristic peaks, crystallinity, and to compare the properties with other carbonaceous forms, i.e. a commercial Carbon Paper (CP), and a commercial meso- carbon micro-beads (MCMB). The analysis found that CWP is dominated by graphitic carbon. An adsorption experiment was then conducted to study their adsorption ability to methyl orange solution. The result found that those three carbonaceous materials have the ability to adsorb methyl orange with different activities. MCMB has the highest adsorption capacity of 0.197 mg.g-1. Meanwhile, CWP and CP show adsorption capacity of 0.066 mg.g-1 and 0.062 mg.g-1, respectively. Methyl orange adsorption on CWP and CP were under second order, which means the adsorption could be four times faster as the MO solution doubled. Moreover, the rate constant of MO adsorption on CWP is 8×10-4 min-1, which was higher than the rate constant of MO adsorption on CP. It confirmed that the CWP can be used as a promising adsorbent for dye waste water. Copyright © 2020 BCREC Group. All rights reserved

El objetivo de esta investigación fue la reducción de las trazas de materia orgánica en el agua potable por medio del uso de zeolita natural, zeolita activada y la comparación con la eficiencia de la adsorción del carbón activado. Se utilizó agua suministrada por la compañía AGUAPEN E.P. y materiales adsorbentes zeolita natural, zeolita activada y carbón activado. La zeolita se activó térmicamente a 600ªC. Se realizaron pruebas en columnas de adsorción a escala (RSSCT – Rapid Small-Scale Column Test) para carbón activado granular (GAC) de acuerdo a la norma ASTM 6586 para determinar la eficiencia de la adsorción de las trazas de materia orgánica en el agua potable. Se determinó la eficiencia en base al parámetro de carbono orgánico total en muestras simple del afluente y efluente del agua tratada cada 3 horas durante 24 horas. El incremento de la presión de trabajo evidencia el punto de ruptura o colmatación del adsorbente. La concentración del Carbón Orgánico Total (COT) se determinó mediante el análisis de la combustión de la muestra con el detector infrarrojo no dispersivo de dióxido de carbono (CO2). Los resultados mostraron reducción de materia orgánica con el uso de zeolita natural y zeolita activada, con respecto al carbón activado.AbstractThe objective of this research was the reduction of organic matter traces in drinking water through the use of natural and activated zeolite, and the comparison with the efficiency of activated carbon adsorption. Water supplied by the company AGUAPEN E.P. was used, and adsorbent materials as natural zeolite, activated zeolite and activated carbon were utilized. The zeolite was thermally activated at 600 ° C. Tests were performed on scale adsorption columns (RSSCT - Rapid Small Scale Column Test) for Granular Activated Carbon (GAC) according to ASTM 6586 to determine the efficiency of the adsorption of traces of organic matter in drinking water. Efficiency was determined based on the total organic carbon parameter in simple affluent and effluent samples of treated water every 3 hours during 24 hours. The increase in working pressure shows the point of rupture or clogging of the adsorbent. The concentration of Total Organic Carbon (TOC) was determined by analyzing the sample combustion with a non-dispersive infrared carbon dioxide (CO2) detector. The results showed the reduction of organic matter in natural zeolite and activated zeolite compared to activated carbon.

Labile carbon (C) is a major source of C loss because of its high vulnerability to environmental change. Yet its potential role in regulating soil organic carbon (SOC) dynamics remains unclear. In this study, we tested the effect of physical disturbance on SOC decomposition using soils from two abandoned farmlands free of management practice for more than 28 years. The soil respiration rate was measured in undisturbed and disturbed soil columns and was inversely modeled using the two-compartment model. We found that the C loss was 16.8~74.1% higher in disturbed than in undisturbed soil columns. Physical disturbance increased the total amount of labile C (C₁) loss by 136~241%, while had no effect on the kinetic decomposition rate constants of both labile (k₁) and stable (k₂) SOC decomposition. Physical disturbance fragmented the large macroaggregates into small macroaggregates, microaggregates, and free silt and clay-sized fractions. This indicates that C loss was derived from the initially protected labile C, and there was no change of SOC fraction being decomposed. Our results give insights into the understanding of the extent of labile C loss to physical disruption and demonstrate the potential effect of physical disturbance on SOC dynamics.

Adsorption studies of Na+, Cs+, Ag+, Sr2+ and Co2+ from aqueous solutions by surface-treated activated carbons are reported. Carbon–oxygen and carbon–nitrogen surface complexes were formed on an activated carbon from almond shells by treating it with either oxidizing reagents or ammonia. In order to discover the surface acidity and/or basicity of each carbon, selective neutralization techniques were carried out. Both Na+ and Cs+ are adsorbed by only those carbons containing strong acidic functional groups; however, Ag+, Sr2+ and Co2+ are adsorbed not only by these latter carbons but also by those with predominance of basic groups. The results suggest that some of these carbons can be used to remove, separate and pre-concentrate all the cations studied.

Activated carbon and five kinds of metal-ion-substituted activated carbons, viz. Ag+-activated carbon, Cu2+-activated carbon, Fe3+-activated carbon, Ba2+-activated carbon and Ca2+-activated carbon, were prepared. A model for estimating the activation energy of desorption was established. Temperature-programmed desorption (TPD) experiments were conducted to measure the TPD curves of n-hexanol and hence estimate the activation energy for n-hexanol desorption from the various activated carbons. The results showed that the activation energies for n-hexanol desorption from the Ag+-activated carbon, the Cu2+-activated carbon and the Fe3+-activated carbon were higher than those from the unsubstituted activated carbon, the Ca2+-activated carbon and the Ba2+-activated carbon.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007.
Vita.
Includes bibliographical references.
This thesis presents work towards the development of a new catalytic C-C bond forming reaction. Alkynes and olefins insert into [(IPr)CuH]2 (IPr = N,N-bis-(2,6-diisopropylphenyl)-1,3-imidazol-2-ylidene) to give copper vinyl and copper alkyl complexes. These copper complexes insert CO2 into the Cu-C bond to form copper acrylate and copper carboxylate complexes. Acrylic and carboxylic acids can be isolated by hydrolysis. A catalytic cycle based on (IPr)copper(I) was developed. Alkynes undergo reductive carboxylation to give acrylic acids in moderate yields. Unexpected interactions between several components of the catalytic system led to a number of side reaction, most importantly between [(IPr)CuH]2 and the product silyl acrylate. The use of silylcarbonate salts to desylilate the product enhanced yield. In addition, silylcarbonates can also serve as a source of CO2.
by Gergely Sirokman.
Ph.D.

El balanç entre l´entrada de C (dels residus vegetals) i sortides de C (principalment com CO2 de la descomposició del carboni orgànic del sòl -SOC-), determina el contingut de SOC, que és el depòsit de C més voluminós a la superfície terrestre. Als agroecosistemes semiàrids Mediterránis, l’aigua és el principal factor limitant del creixement del cultiu i de l´entrada de residus al sòl. Les pràctiques agronòmiques alternatives poden millorar el creixement vegetal i augmentar la quantitat de residus (entrada de C) en aquestos sistemes. No obstant això la resposta del contingut de SOC dependrà del balanç de les entrades amb les sortides de C. Aquest treball estudia els efectes de l’adopció a llarg termini de sistemes de conreu (NT, sembra directa; MT, mínim conreu CT, conreu convencional) i del nivell de fertilizació nitrogenada (zero; mitjà, 60 kg N ha-1; alt, 120 kg N ha-1) al balanç de C del sòl i el contingut de SOC. El contingut de SOC augmentà finalment 4.3 i 3.9 Mg C ha-1 sota NT repecte a MT i CT. Nivells mitjans i alts de fertilització nitrogenada augmentaren el contingut de SOC en 3.4 i 4.5 Mg C ha-1 respecte al contingut a les parcel•les no fertilitzades. L´adopció a llarg termini de pràctiques de conreu de conservació (sembra directa), juntament amb l’ús adequat de la fertilització nitrogenada van demostrar ser eines per a millorar la sostenibilitat dels nostres secans i emmagatzemar C al sòl.
El balance entre la entrada de C (de los residuos vegetales) y salidas de C (principalmente como CO2 de la descomposición del carbono orgánico del suelo -SOC-), determina el contenido de SOC, que es el mayor depósito terrestre de C. En agroecosistemas semiáridos Mediterráneos, el agua es el principal factor limitante del crecimiento del cultivo y de la entrada de residuos en el suelo. Las prácticas agronómicas alternativas pueden mejorar el crecimiento vegetal y aumentar la cantidad de residuos (entrada de C) en estos sistemas. Este trabajo estudió los efectos de la adopción a largo plazo de sistemas de laboreo (NT, no-laboreo; MT, laboreo minimo; CT, laboreo convencional) y del nivel de fertilización nitrogenada (cero; medio, 60 kg N ha-1; alto, 120 kg N ha-1) en el balance de C del suelo y el contenido de SOC. El contenido de SOC aumentó en 4.3 y 3.9 Mg C ha-1 bajo NT con respecto a MT y CT. Niveles medios y altos de fertilización nitrogenada aumentaron el contenido de SOC en 3.4 y 4.5 Mg C ha-1 con respecto al contenido en las parcelas no fertilizadas. La adopción a largo plazo de prácticas de laboreo de conservación (no-laboreo o siembra directa), junto con el uso adecuado de la fertilitzación nitrogenada demostraron ser herramientas para mejorar la sostenibilidad de los secanos semiáridos Mediterráneos y almacenar C en el suelo.
The balance between C inputs (from plant residues) and C outputs (mainly as CO2 from soil organic carbon -SOC- decomposition) determines the content of SOC which is is the largest terrestrial reservoir of carbon. Under semiarid Mediterranean agroecosystems, water limitation restrains plant growth and the return of crop residues to the soil. Alternative agronomical practices may improve crop growth and increase return of crop residue (C inputs) under these systems. This work studied the effects of long term adoption of tillage practices (NT, no-tillage; MT, minimum tillage; CT, conventional tillage) and nitrogen (N) fertilization level (zero; medium, 60 kg N ha-1; high, 120 kg N ha-1) on the SOC balance and the content of SOC. The stock of SOC was increased by 4.3 and 3.9 Mg C ha-1 under NT in comparison to MT and CT respectively. Long-term medium and high N fertilization increased the stock of SOC by 3.4 and 4.5 Mg C ha-1 in contrast to unfertilized plots. Long-term adoption of conservation tillage practices (no-tillage) together with adequate N fertilizer use, proved to be effective tools to improve sustainability of semiarid Mediterranean drylands and to store C in the soil.

Thesis (M. S.)--Chemical Engineering, Georgia Institute of Technology, 2009.
Committee Chair: Dr. Christopher Jones; Committee Co-Chair: Dr. Pradeep Agrawal; Committee Member: Dr. Sujit Banerjee; Committee Member: Dr. Tom Fuller. Part of the SMARTech Electronic Thesis and Dissertation Collection.

The thesis is composed of two parts. Part I presents catalytic C-C, C-N, C-O bond formation: a series of dienylethers, 2,5-disubstituted furans, allylketones, γ-functionalized ketones, multisubstituted quinolines were made starting from terminal alkynes with the initial help of a ruthenium catalyst. Part II presents C-C, C-N, C-O bond formation reactions: a variety of tetrahydropyrimidines, and 1,3-oxazines were synthesized starting from electron-deficient alkynes via multiple component reactions
La thèse est composée de deux parties. La partie I présente la formation catalytique de liaisons C-C, C-N et C-O : une série d’ethers, de diényle, furanes 2,5-disubstitués, cétones allyliques et γ-fonctionalisées et quinolines polysubstituées ont été préparées à partir d’alcynes avec l’aide initiale d’un catalyseur de ruthenium. La partie II présente la formation de liaisons C-C, C-N, C-O: une variété de tetrahydropyridines, et de 1,3-oxazines ont été synthétisées à partir d’alcynes electrophiles via des réactions à composants multiples

Ce travail de thèse présente le développement de nouvelles réactions de formation de liaisons carbone-carbone. Le premier chapitre décrit la cyanation d’arylzinciques par catalyse au cobalt à partir d’une source non toxique et bénigne, le N-cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS), et conduit à de bons rendements en benzonitriles correspondants. Dans cette réaction, le cobalt sert de catalyseur non seulement pour la formation des arylzinciques mais aussi pour la formation de liaisons C-CN. Les groupements fonctionnels, cétone et nitrile, sont permis lorsque le complexe de cobalt associé au ligand bipyridine est utilisé. Le deuxième chapitre porte sur l’homocouplage Csp3-Csp3. Un simple halogénure de cobalt permet de catalyser la dimérisation des halogénures d’alkyles et des acétates d’allyles avec de bons à d’excellents rendements. L’ajout d’iodure de sodium permet d’étendre cette réaction aux chlorures et tosylates d’alkyles. Le couplage croisé entre 2 halogénures d’alkyle différents a également été testé mais les conditions doivent être optimisées. Dans le troisième chapitre, le couplage croisé catalysé au cobalt entre des bromures vinyliques et des chlorures benzyliques est présenté. Des halogénures de vinyles et de benzyles porteurs de groupements electrodonneurs ou electroattrateurs peuvent ainsi être couplés efficacement avec rétention de la configuration de la double liaison. Un mécanisme radicalaire semble être impliqué. Enfin, le dernier chapitre décrit l’arylation d’une 2-phenylpyridine avec un arylzincique par catalyse au cobalt par activation d’une liaison C-H et conduit à de premiers résultats encourageants
This thesis presents the development of cobalt-catalyzed carbon-carbon bonds formation. The first chapter describes a novel cobalt-catalyzed electrophilic cyanation of arylzinc species, employing benign and non-toxic N-cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS) as the cyano source. In this reaction, cobalt catalyzes both the formation of arylzinc species and the cyanation reaction. Various benzonitriles are synthesized affording good to excellent yields. Using cobalt-bipyridine complexes instead of CoBr2, ketone and nitrile groups can be tolerated. The second chapter reports cobalt-catalyzed Csp3-Csp3 homocoupling reaction. A simple catalytic system could deliver dimers of a number of alkyl halides/pseudohalides and allylic acetates. Sodium iodide is crucial for the homocoupling of unactivated alkyl chlorides and tosylates. This method is extended to alkyl-alkyl cross-coupling; however, the conditions still need to be optimized. The third chapter describes a cobalt-catalyzed vinyl-benzyl cross-coupling. A variety of functionalized vinyl bromides and benzyl chlorides are efficiently coupled under mild conditions in good to excellent yields, with retention of Z/E configuration. A few mechanistic experiments indicate a single electron transfer involved. The last chapter discusses the progress on the cobalt-catalyzed arylation of 2-phenylpyridine with an arylzinc species by C-H activation and promising results are obtained

2013/2014
La nanotecnologia è chiamata a rivoluzionare molti settori della nostra vita. Tra tutti i campi in cui è convolta, la ricerca delle energie rinnovabili, la possibilità di ottenere acqua pulita in tutte le parti del mondo, il miglioramento della salute e l’aumento dell’aspettativa di vita e lo sviluppo di sistemi informatici, sono gli obiettivi che si distinguono. Le nanostrutture di carbonio sono materiali promettenti che possono aiutare a raggiungere questi obiettivi: includono fullereni, grafene, nanotubi e nanohorns di carbonio. Tutti hanno proprietà interessanti e offrono nuovi vantaggi per le applicazioni in chimica dei materiali e nella medicina. Il nostro gruppo di ricerca ha sviluppato interessanti metodi per modificare queste nanostrutture per poterli applicare nei campi sopra menzionate. In questo contesto, lo scopo generale di questa tesi è il disegno di sistemi multifunzionali basati su nanostrutture di carbonio destinati ai sensori e alle applicazioni biologiche. Nel capitolo 1, viene fatta una breve panoramica dei nanotubi e i nanohorns di carbonio, spiegando la loro struttura, le loro proprietà e le loro applicazioni. Inoltre, vengono descritte le diverse strategie per la loro funzionalizzazione. Il riconoscimento molecolare gioca un ruolo importante in molti sistemi biologici. In flavoproteine, l'interazione specifica tra il cofattore flavina e l’apoenzima determina la reattività della proteina. Di conseguenza, la modulazione dell'ambiente delle flavine può essere utilizzata come strumento per determinare il loro comportamento e anche per comprendere i processi molecolari negli enzimi. Con questi obiettivi in mente, nel capitolo 2 è descritta la sintesi di differenti derivati basati sul sistema nanotubi di carbonio-triazina per l’uso come ricevitori di riboflavina. In primo luogo, la sintesi e la caratterizzazione di diverse 1,3,5-triazine sono riportate. In una seconda fase, viene descritta la funzionalizzazione di nanotubi di carbonio a parete singola e a parete multipla con le differenti triazine e anche con catene di p-tolil, impiegando le radiazioni microonde. Dopo, si riporta la caratterizzazione completa di questi derivati con varie tecniche. L’auto-assemblaggio degli ibridi è stato analizzato con microscopia elettronica a trasmissione, osservando come i funzionalizzati con 1,3,5-triazine formano buone dispersioni in acqua, mentre loro si auto-assemblano in solventi non polari a causa del riconoscimento di legami d’idrogeno complementari. Tuttavia, derivati funzionalizzati con p-tolil formano migliori dispersioni in solventi organici ed invece si auto-assemblano in acqua. Viene poi studiata la capacità dei nanotubi di carbonio funzionalizzati a parete multipla di riconoscere la riboflavina con la spettroscopia di fluorescenza e ultravioletta visibile, analizzando la grandezza delle interazioni non-covalenti. Si vede come la funzionalizzazione covalente dei nanotubi di carbonio diminuisce la loro capacità di formare interazioni  mentre le interazioni di legame d’idrogeno giocano un ruolo fondamentale nel processo di riconoscimento tra i membri del sistema. Inoltre, si è demostrata l’influenza dei tipi di triazine nel comportamento della riboflavina. In questo modo, è dimostrata la modulazione del riconoscimento molecolare della riboflavina attraverso i diversi nanotubi. Così, recettori artificiali in processi di catalisi possono essere specificamente disegnati per ottenere il controllo delle interazioni tra i nanotubi di carbonio funzionalizzati e la riboflavina, modificando il suo comportamento. Inoltre, le dimensioni e le eccellenti proprietà di nanotubi permettono di utilizzarli come strumento nella progettazione di sensori per la rivelazione di singole molecole. Nel capitolo 3 si riporta la modifica di nanohorn di carbonio per l'impiego come farmaci selettivi nella terapia del cancro è rapportata. Prima, si mostra la sintesi e la caratterizzazione di diversi ibridi di nanohorn: Antibody-CNH, Drug-CNH, Antibody-Drug-CNH e Double Functionalized-CNH. In particolare vengono usati cisplatino, come profarmaco, ed un anticorpo specifico per le cellule che mostrano l’antigene PSMA (Prostate-specific membrane antigen). Di seguito, vengono presentati diversi esperimenti biologici sviluppati in collaborazione con il professor Marco Colombatti dell’Università degli Studi di Verona (Italia). L’ibrido Antibody-Drug-CNH possiede una migliore capacità di uccidere selettivamente le cellule che presentano l'antigene PSMA, rispetto ad altri derivati di nanohorns. Il nuovo sistema progettato offre un grande potenziale dato dalla possibilità di modificare il tipo e il grado di funzionalizzazione. Questo permette di variare la quantità di farmaco o di anticorpo nelle nanostrutture con lo scopo di migliorare l’efficienza dei nuovi derivati. Inoltre, questo metodo può incorporare altri farmaci o anticorpi al sistema, aprendo la porta al trattamento di altre malattie. Il capitolo 4 descrive l'applicazione di diverse nanostrutture di carbonio nella terapia genica. Prima, si mostra la funzionalizzazione di nanohorns di carbonio con gruppi amminici, impiegando diversi metodi che utilizzano le radiazioni a microonde (cicloaddizione 1,3-dipolare e addizione radicalica). In seguito, viene presentato il lavoro svolto in "the Nanomedicine Lab" (Università di Manchester), sotto la supervisione del Prof. Kostas Kostarelos. L'efficacia dei nanohorns di carbonio funzionalizzati per formare complessi con siRNA è comparata con quella dei nanotubi di carbonio forniti dal gruppo del professor Kostarelos. Si è visto come i nanohorn di carbonio formino complessi con siRNA a differenza dei nanotubi. I complessi siRNA/nanohorn si caratterizzano utilizzando varie tecniche e viene analizzata la loro capacità di rilasciare il siRNA. Sebbene nanohorn di carbonio funzionalizzati con l’addizione radicalica mostrano una forte interazione con il materiale genetico, i derivati funzionalizzati con la cicloaddizione 1,3-dipolare lo rilasciano più facilmente. I risultati suggeriscono che, per conseguire il miglior carrier, la complessazione totale del siRNA con le nanostrutture dovrebbe essere evitato. Tuttavia, gli ibridi devono essere analizzati in vitro per garantire la migliore scelta. Questo studio contribuisce alla comprensione dell’uso di nanohorn di carbonio come vettori per terapia genica; ma, un maggior numero di derivati deve essere analizzato per un confronto completo con i nanotubi di carbonio.
La nanotecnología se presenta como una nueva ciencia que podrá revolucionar multiples aspectos de nuestras vidas. Entre los numerosos campos en los que la nanotecnología está centrada, la búsqueda de energías renovables, la posibilidad de obtener agua limpia en cualquier parte del mundo, la mejora de la salud y la longevidad de las personas así como el avance de los sistemas informáticos, son los objetivos que más destacan. Las nanoestructuras de carbon son nanomateriales prometedores que pueden ayudar a lograr esas metas. Estos materiales incluyen fullerenos, grafeno, nanohorns y nanotubos de carbono, entre otros. Todos ellos presentan propiedades interesantes y ofrecen nuevas ventajas para aplicaciones en química de materiales y medicina. Nuestro grupo de investigación ha desarrollado metodologías interesantes para la modificación de esas nanoestructuras con el objeto de que puedan ser útiles en las aplicaciones citadas anteriormente. En ese contexto, el objetivo general de esta tesis es el diseño de sistemas multifuncionales basados en nanoestructuras de carbono para ser usados en sensores y en aplicaciones biológicas. En el capítulo 1 se detallan la estructura y las propiedades de los nanohorns y los nanotubos de carbono junto a sus aplicaciones. Además, se muestra un resumen de las diferentes metodologías usadas para su funcionalización. El reconocimiento molecular juega un papel importante en numerosos sistemas biológicos. En flavoproteinas, la interacción específica entre el cofactor flavina y la apoenzima determina la reactividad total de la proteina. De este modo, la modulación del entorno de la flavina puede usarse como herramienta para determinar su comportamiento y, además, para entender los procesos moleculares en las enzimas. Con esos objetivos en mente, en el capítulo 2 se describe la síntesis de diferentes derivados basados en el sistema nanotubo de carbono-triazina para usarlos como receptores múltiples de riboflavina. En primer lugar, se sintentizan y caracterizan distintas 1,3,5-triazinas. En un segundo paso, se funcionalizan nanotubos de carbono tanto de pared simple como de pared multiple con las diferentes triazinas así como con cadenas de p-tolilo usando radiación microondas, y esos derivados se caracterizan completamente mediante diversas técnicas. El autoensamblaje de los híbridos se analiza mediante microscopía de transmisión electrónica observando como los derivados de 1,3,5-triazinas forman buenas dispersiones en agua y se autoensamblan en disolventes no polares debido al reconocimiento mediante enlaces de hidrógeno complementarios. Sin embargo, los derivados de p-tolilo forman mejores dispersiones en disolventes orgánicos y se agregan en agua. Finalmente, la habilidad de los nanotubos de carbono de pared múltiple funcionalizados para reconocer la riboflavina se estudia mediante fluorescencia y espectrocopía ultravioleta visible, analizando el alcance de las interacciones no covalentes. La funcionalización covalente de nanotubos de carbono disminuye su habilidad para formar interacciones  mientras que las interacciones mediante enlaces de hidrógeno juegan un papel fundamental en el proceso de reconocimiento entre los componentes del sistema. También se estudia la infuencia de las diferentes triazinas en el comportamiento de los complejos. De esta manera, se demuestra la modulación del reconocimiento de la riboflavina por medio de los diversos híbridos de nanotubos de carbono. Así, los receptores artificiales en procesos de catálisis pueden ser específicamente diseñados para lograr control de la interacción entre los nanotubos de carbono funcionalizados y la riboflavina, modificando así su comportamiento. En el capítulo 3 se describe la modificación de nanohorns de carbon para ser usados como fármacos selectivos en la terapia contra el cancer. En primer lugar se muestra la síntesis y caracterización de diferentes híbridos de nanohorns: Antibody-CNH, Drug-CNH, Antibody-Drug-CNH and Double Functionalized-CNH. En particular se usan cisplatino en forma de prodroga y un anticuerpo específico (D2B) para células de próstata que muestran el antígeno PSMA. Finalmente se presentan diferentes experimentos biológicos desarrollados en colaboración con el profesor Marco Colombatti, de la Universidad de Verona (Italia). Se demuestra la mejor habilidad del híbrido Antibody-Drug-CNH para matar selectivamente células que muestran el antígeno PSMA en comparación con los otros derivados de nanohorns. El nuevo sistema diseñado ofrece gran potencial debido la la posibilidad de modificar tanto el tipo como el grado de funcionalización. Esto permite variar la cantidad de fármaco o anticuerpo en la nanoestructura con el objetivo de conseguir una mejor eficacia del derivado. Además, con este método se pueden incorporar otros fármacos o anticuerpos al sistema, lo que abre la puerta al tratamiento de otras enfermedades. El capítulo 4 describe la aplicación de distintas nanoestructuras de carbono en terapia génica. Primero se muestra la funcionalización de nanohorns de carbono con grupos amino mediante diferentes metodologías usando radiación microondas (cicloadición 1,3-dipolar y adición radicálica). Después, se presenta el trabajo desarrollado en “the Nanomedicine Lab” (Universidad de Manchester) bajo la supervision del profesor Kostas Kostarelos. Se compara la eficacia de los nanohorns de carbono funcionalizados para formar complejos con siRNA con la de una serie de nanotubos de carbono aportados por el grupo del profesor Kostarelos. En nuestros experimentos, los nanohorns de carbon forman complejos mejor que los nanotubos. Los complejos siRNA/nanohorns se caracterizan mediante diversas técnicas y se analiza su capacidad de liberar el siRNA. Aunque los nanohorns de carbono funcionalizados mediante adición radicálica muestran una interacción más fuerte con el material genético, los derivados funcionalizados mediante cicloadición 1,3-dipolar lo liberan de manera más fácil. Los resultados sugieren que la complejación total entre el siRNA y la nanoestructura debe ser evitada para lograr más fácilmente el posterior desplazamiento de este dentro de la célula. Sin embargo, para garantizar la elección del híbrido más eficaz, los complejos deben ser analizados in vitro. Por tanto, este estudio contribuye al entendimiento de los nanohorns de carbono como vectores en terapia génica. No obstante, un mayor número de derivados deben ser analizados para lograr una comparación completa con los nanotubos de carbono.
Nanotechnology is claimed to revolutionize every aspect of our life. Among the large number of fields in which nanotechnology is involved; finding renewable clean energy, obtaining clean water for all, improving health and longevity and enhancing computing power are the most noteworthy. Carbon nanostructures are promising nanomaterials that can help to achieve these objectives. Fullerenes, graphene, nanohorns and nanotubes are including within these materials. All of them exhibit interesting properties and offer new opportunities for applications in material chemistry and medicine. Our research group has developed interesting methodologies for modifying these nanostructures in order to be used in the aforementioned applications. In this context, the objective of this thesis is the design of multifunctional systems based on carbon nanomaterials to be applied in sensors and in biological applications. Chapter 1 explains the structure, properties and applications of carbon nanohorns and carbon nanotubes, together with their applications. In addition, it provides an overview of the different methodologies to functionalize them. Molecular recognition plays an important role in numerous biological systems. In flavoproteins, the specific interaction between the flavin cofactor and the apoenzyme determines the reactivity of the entire protein. Therefore, the modulation of the environment of flavins can be used as a tool to set their behaviour and to understand the molecular processes in enzymes. With these aims, chapter 2 describes the synthesis of different carbon nanotubes-triazine derivatives to be used as multi-receptors of riboflavin. Firstly, different triazines are synthesized and characterized. In a second step, both single-walled and multi-walled carbon nanotubes are functionalized with different 1,3,5-triazine and p-tolyl chains using radical addition under microwave irradiation and these derivatives are characterized by different techniques. The self-assembly of these hybrids is analysed by transmission electron microscopy, observing how the 1,3,5-triazines derivatives form good dispersions in water and self-assemble in non-polar solvents due to the DAD-ADA hydrogen bonding recognition, while the p-tolyl derivatives show better dispersability in organic solvents and aggregate in polar solvents. Finally, the ability of the functionalized multi-walled carbon nanotubes to recognize riboflavin is studied by fluorescence and UV spectroscopy, analysing the scope of the different non-covalent interactions. It is shown that the functionalization of nanotubes by covalent approach decreases the ability of them to form  stacking and also that the hydrogen bond interactions play an important role in the recognition processes between the components. The influence of the different triazines in the complexes is also shown. Thus, the modulation of the molecular recognition of riboflavin by the diverse nanotubes hybrids is demonstrated. Therefore, our study clarifies the understanding of non-covalent interactions in biological systems. In this way, artificial receptors in catalystic processes could be designed through a specific control of the interaction between functionalized carbon nanotubes and riboflavin. Additionally, the size and the excellent properties of carbon nanotubes will permit to use them as the building blocks in the design of sensors for single-molecule detection. In chapter 3, the modification of carbon nanohorns to be applied as new selective drugs in cancer therapy is shown. Firstly, the synthesis and characterization of different conjugates by the functionalization of carbon nanohorns with orthogonal chains is reported: Antibody-CNH, Drug-CNH, Antibody-Drug-CNH and Double Functionalized-CNH. In particular, cisplatin in a prodrug form and a specific D2B antibody for PSMA+ prostate cancer cells are attached. In collaboration with the group of Professor Marco Colombatti, different biological experiments are reported. The better ability of Antibody-Drug-CNH to selectively kill PSMA+ cancer cells in comparison with the other synthesized CNHs hybrids is demonstrated. This new system offers great potentiality due to the possibility of modifying the type and degree of functionalization. This allows the variation of the quantity of drug or antibody attached to the nanostructure in order to play with the killing efficacy. Similarly, the method is useful to attach different drugs or antibodies opening the way to the treatment of other diseases. Chapter 4 describes the application of different carbon nanostructures in gene delivery. Firstly, the functionalization of carbon nanohorns with amino moieties by different methodologies (1,3-dipolar cycloaddition and radical addition) under microwave irradiation and their characterization is shown. Then, the work developed at the Nanomedicine Lab (University of Manchester) under the supervision of Professor Kostas Kostarelos is reported. The efficacy of the functionalized carbon nanohorns to form complexes with siRNA is compared with the one of functionalized carbon nanotubes provides by Prof. Kostarelos’s group. In our experiments, carbon nanohorns form complexes better than nanotubes. The nanohors complexes are characterized by different techniques and their capability to release siRNA is analysed. Although the carbon nanohorns functionalized by radical addition showed the strongest complexation of siRNA, the derivatives functionalized by 1,3-dipolar cycloaddition showed its easiest release. The results suggest that, in order to obtain the best candidate, a complete complexation of siRNA with the carrier should be avoided. However, the analysis of the cellular uptake should be evaluated in the future to assess the greatest candidate. These outcomes contribute to the understanding of the role of carbon nanohorns as gene delivery vectors. Nevertheless, additional derivatives should be tested for a fully comparison with carbon nanotubes.
XXVII Ciclo
1986