1,3,6,8-Tetrasubstituted Pyrenes: Solution-Processable Materials for Application in Organic Electronics

(Equation Presented). A series of star-shaped organic semiconductors have been synthesized from 1,3,6,8-tetrabromopyrene. The materials are soluble in common organic solvents allowing for solution processing of devices such as light-emitting diodes (OLEDs). One of the materials, 1,3,6,8-tetrakis(4- butoxyphenyl)pyrene, has been used as the active emitting layer in simple solution-processed OLEDs with deep blue emission (CIE = 0.15, 0.18) and maximum efficiencies and brightness levels of 2.56 cd/A and >5000 cd/m2, respectively.

Epoxy composites containing cobalt(II)-porphine anchored multiwalled carbon nanotubes as thin electromagnetic interference shields, adhesives and coatings

Herein a facile strategy has been adopted to design epoxy based adhesive/coating materials that can shield electromagnetic radiation. Multiwalled carbon nanotubes (MWNTs) were non-covalently modified with an ionic liquid and 5,10,15,20-tetrakis(4-methoxyphenyl)-21H,23H-porphine cobalt(II) (Co-TPP). The dispersion state of modified MWNTs in the composites was assessed using a scanning electron microscope. The electrical conductivity of the composites was improved with the addition of IL and Co-TPP. The shielding effectiveness was studied as a function of thickness and intriguingly, composites with as thin as 0.5 mm thickness were observed to reflect 497% of the incoming radiation. Carbon fibre reinforced polymer substrates were used to demonstrate the adhesive properties of the designed epoxy composites. Although, the shielding effectiveness of epoxy/MWNT composites with or without IL and Co-TPP is nearly the same for 0.5 mm thick samples, the lap shear test under tensile loading revealed an extraordinary adhesive bond strength for the epoxy/IL-MWNT/Co-TPP composites in contrast to neat epoxy. For instance, the lap shear strength of epoxy/IL-MWNT/Co-TPP composites was enhanced by 100% as compared to neat epoxy. Furthermore, the composites were thermally stable for practical utility in electronic applications as inferred from thermogravimetric analysis.

MOFs basados en metaloporfirinas: diseño estructural orientado a la biomimetización de sus propiedades naturales

La Ciencia y Tecnología de Materiales tiene el reto permanente de desarrollar y mejorar materiales multifuncionales y respetuosos con el medio ambiente. En este sentido, los materiales de tipo MOF (Metal-Organic Framework) están siendo objeto de un gran interés, ya que las redes sólidas de coordinación (especialmente, las porosas) presentan aplicaciones en campos en los que la sociedad manifiesta una demanda creciente de ciencia y tecnología, como el almacenamiento y transporte de energía, la captura de gases con efecto invernadero, la catálisis heterogénea y la liberación controlada de fármacos, entre otros. En este contexto, el presente trabajo se planteó con el objetivo de desarrollar nuevos materiales de tipo MOF basados en metaloporfirinas, al objeto de mimetizar las funciones que desempeñan las mismas en los sistemas biológicos, con el fin de reproducirlas en el estado sólido. Para ello, se han escogido biometales como el hierro y el cobalto: característicos de estos sistemas, de bajo coste y medioambientalmente respetuosos. Por otra parte, las porfirinas seleccionadas han sido las siguientes: TPP (meso-tetra-4-fenilporfirina), TCPP (meso-tetra-4-carboxifenilporfirina) y TPPS (meso-tetra-4-sulfonatofenilporfirina). Estas tres moléculas conforman un conjunto de ligandos que difieren ligeramente en sus grupos funcionales. Asimismo, en ocasiones, se ha utilizado un ligando secundario dipiridínico (4,4´-bipiridina) que ha actuado como espaciador. El diseño de las síntesis se ha centrado tanto en las combinaciones adecuadas de metales y ligandos como en la selección de las técnicas de síntesis. Así, se han obtenido cinco nuevos compuestos, que se han sintetizado en condiciones solvotermales suaves o mediante radiación microondas. La caracterización preliminar de los mismos se ha llevado a cabo mediante análisis cuantitativo, espectroscopia infrarroja y Raman, difracción y fluorescencia de rayos X y medidas de densidad. El estudio estructural se ha realizado mediante difractometría de rayos X y el estudio térmico se ha llevado a cabo mediante termogravimetría y termodifractometría. En los casos en que ha resultado procedente, también se han caracterizado los compuestos mediante espectroscopia ultravioleta-visible (UV-Vis), Mössbauer y resonancia paramagnética electrónica (EPR) y mediante medidas de la susceptibilidad magnética. Asimismo, ocasionalmente, se han realizado cálculos mecano-cuánticos basados en la teoría del funcional de la densidad (DFT) y medidas catalíticas. El primero de los cinco compuestos obtenidos, de fórmula [FeTCPP], es quiral y destaca por ser la tercera estructura 2D publicada basada en esta porfirina. La formación de este compuesto está condicionada por la oxidación de los iones de hierro y por la existencia de grupos carboxílicos en la porfirina. Por otra parte, con la participación del espaciador 4,4´-bipiridina (bipy) se han obtenido tres redes 1D. Así, la estructura cristalina del compuesto ([FeTPPbipy]•)n se explica mediante la formación de radicales neutros que se estabilizan en un empaquetamiento que permite la formación de enlaces entre los grupos fenílicos de distintas cadenas. La formación de estos enlaces queda corroborada por la existencia de significativas interacciones antiferromagnéticas. Por otra parte, en el compuesto [CoTPP(bipy)]•([CoTPP])0.22•(TPP)0.78, la disposición de las cadenas deja grandes huecos en la red que se ocupan con porfirinas tanto coordinadas como sin coordinar. El tercero de estos compuestos 1D presenta la fórmula [CoTPPS0.5(bipy)(H2O)2]•6H2O y destaca porque la extensión de las cadenas se produce por la alternancia de dos tipos de octaedros de CoII. La naturaleza de los grupos sulfonato de la porfirina TPPS es determinante para comprender la intrincada red de enlaces de hidrógeno de este compuesto, que propician la formación de una red interpenetrada caracterizada por su gran estabilidad térmica (hasta los 370ºC). Finalmente, con la porfirina TCPP se ha obtenido un segundo compuesto de fórmula -O-[FeTCPP]2•nDMF (n≈ 16; DMF = dimetilformamida). El mismo presenta grandes cavidades (47% de porosidad) que diluyen la matriz magnética, caracterizada por fuertes interacciones antiferromagnéticas intradiméricas. Todo ello revela una inusual estructura superhiperfina, observada por espectroscopia EPR. El trabajo que se recoge en esta memoria constituye, por lo tanto, un “viaje” de mayor a menor dimensionalidad en las estructuras cristalinas. La guía de este viaje ha sido la búsqueda de propiedades catalíticas en sistemas heterogéneos. Así, el [CoTPP(bipy)]•([CoTPP])0.22•(TPP)0.78 obedece el enfoque de inmovilizar o anclar el catalizador en los huecos de la red. Sin embargo, la estrategia alternativa seguida para el compuesto m-O-[FeTCPP]2•nDMF (es decir, que el propio MOF actúe de catalizador) es la que ha aportado mejores y más prometedores resultados en lo que a catálisis heterogénea se refiere.

Auto-ensamblaje de unidades porfirínicas para la obtención de dispositivos supramoleculares

Comunicación presentada en: II Reunión de Jóvenes Cristalógrafos, 29 Sept-1 Oct de 2010, Bilbao, España

MOFS metaloporfirínicos 1D y 2D: Estudio cristaloquímico

Comunicación a congreso (póster): XXIV Simposio del Grupo Especializado de Cristalografía y Crecimiento Cristalino, GE3C. 23-26 de junio de 2014, Bilbao

A method to identify the collapse of monolayers at the air-water interface

The collapse behaviour of phthalocyanine monolayers at the air-water interface was studied by means of compression-expansion isotherms. Measurements of two cycles of compression-expansion isotherms of copper tetrakis (4'-benzyloxy-4-phenylsulfonylphenoxy) phthalocyanine showed that the difference in the area per molecule at target pressure between the first cycle and the second cycle was dependent on the target pressure. This difference was used to identify the collapse of monolayers at the air-water interface. The transfer behaviour of monolayers at the air-water interface onto a substrate at different target pressures was also studied.

RESONANCE RAMAN INVESTIGATION OF PH-DEPENDENT EQUILIBRIA OF WATER-SOLUBLE IRON PORPHYRINS

Resonance Raman spectroscopy has been used to probe the structures of; tetrakis(1-methylpyridinium-4-yl)-porphinatoiron(III), FeIII (T4MPyP); tetrakis(1-methylpyridium-2-yl)porphinatoiron(III), FeIII (T2MPyP); tetrakis(4-sulphonatophkenyl)porphinatoir(III), FeIII(TSPP); and tetrakis(4-carboxylatophenyl)porphinatoiron(III), FeIII(TCPP), over a wide pH range. The anionic complexes FeIII (TSPP) and FeIII (TCPP) contain high-spin iron(III) at all pHs. Both these complexes exhibit marked spectral changes at ca. pH 6 which correspond to conversion from the diaquo species, in acid solution, to hydroxy- or mu-oxo dimer complexes. Both cationic complexes show similar diaquo to high-spin hydroxy, or mu-oxo dimer, transitions at ca. pH 6. However, at pH > 11.5 for FeIII (T4MPyP) and pH > 9 for FeIII (T2MPyP) a second equilibrium process is observed, leading to two new species. One of these is readily assigned as the low-spin iron(III) dihydroxy complex by analogy with spectra of the dicyano complex. The second species is assigned to the hydroxy iron(II) complex by comparison with photo-chemically generated FeII (T4MPyP) (OH). The formation of iron(II) species in alkaline solutions of FeIII (T4MPyP) and FeIII (T2MPyP) is entirely unexpected and the significance of the observation to previous investigations of the pH-dependent behaviour of these complexes is discussed.

Arenedicarboximide Building Blocks for Fluorescent Photoinduced Electron Transfer pH Sensors Applicable with Different Media and Communication Wavelengths

N-(aminoalkyl)-4-chloronaphthalene-
1,8-dicarboximides 1, N-
(aminoalkyl)-4-acetamidonaphthalene-
1,8-dicarboximides 3 and N,N'-bis(aminoalkyl)-
perylene-3,4:9,10-tetracarboxydiimides
4 show good fluorescent off ±
on switching in aqueous alcoholic solution
with protons as required for fluorescent
PET sensor design. The excitation
wavelengths lie in the ultraviolet
(lmaxˆ345 and 351 nm) for 1 and 3 and
in the blue-green (lmaxˆ528, 492 and
461 nm) for 4; the emission wavelengths
lie in the violet (lmaxˆ408 nm) for 1, in
the blue (lmaxˆ474 nm) for 3 and in the
yellow-orange (lmaxˆ543 and 583 nm)
for 4. Compound 4b shows substantial
fluorescence enhancement with protons
when immobilized in a poly(vinylchloride)
matrix, provided that 2-nitrophenyloctyl
ether plasticizer and potassium
tetrakis(4-chlorophenyl)borate additive
are present to prevent dye crystallization
and to facilitate proton diffusion
into the membrane, respectively.

Síntese e reatividade de benzo-e pirroloporfirinas

O trabalho descrito nesta dissertação envolve estudos de funcionalização de uma pirrolo[3,4-b]porfirina através de reações do tipo cicloadição [4+2]. A metodologia de cicloadição usada permitiu sintetizar duas grandes famílias de compostos: benzoporfirinas e 1,3-dioxopirroloporfirinas. Este documento é composto por três partes distintas. Na primeira parte são tecidas considerações gerais sobre síntese, propriedades e aplicações de porfirinas. Na segunda parte é apresentado o trabalho desenvolvido no âmbito de síntese e reatividade de benzoporfirinas. Numa primeira fase é feita uma revisão bibliográfica sobre síntese de benzoporfirinas e ftalimidas, uma vez que o trabalho prático descrito apresenta compostos contendo estas duas unidades estruturais. Numa segunda fase é descrito o trabalho desenvolvido para a obtenção de uma benzoporfirina derivatizada com uma unidade de ácido ftálico fundida em posições β-pirrólicas, partindo da reação de Diels-Alder entre uma N-metilpirrolo[3,4- b]porfirina e o acetilenodicarboxilato de dimetilo e posterior hidrólise básica do diéster obtido. Seguem-se os estudos que visaram a obtenção de um anidrido porfirínico a partir do ácido ftálico anterior. Esta plataforma sintética foi usada para diversas transformações com diferentes aminas. Destas reações resultaram diferentes unidades benzoporfirínicas, que serão descritas em pormenor. Face às distintas cores apresentadas pelos diferentes compostos sintetizados, foi ainda feita uma análise pormenorizada dos espectros de UV-vis de alguns dos compostos obtidos. Na terceira parte, é apresentado o trabalho realizado no âmbito da síntese de uma 1,3-dioxopirroloporfirina, partindo da reação de Diels-Alder entre a N-metilpirrolo[ 3,4-b]porfirina e oxigénio singleto (1O2). Primeiramente é feita uma revisão bibliográfica sobre o papel do 1O2 em síntese orgânica e sobre reações de oxidação de isoindóis, compostos possuindo uma analogia estrutural com pirroloporfirinas. Segue-se a descrição da síntese de uma N-metil1,3- dioxopirroloporfirina, em que se começa por apresentar a descrição sistemática de todas as experiências levadas a cabo no sentido de otimizar o rendimento do composto em questão, tirando partido da reação com 1O2. Seguidamente expõemse as diferentes abordagens conduzidas para proceder à funcionalização da 1,3- dioxopirroloporfirina obtida. São apresentadas reações de hidrólise e reações com diferentes aminas. As reações com aminas conduziram à formação de porfirina- 2,3-dicarboxamidas e posteriormente às 1,3-dioxopirroloporfirinas correspondentes. Também neste caso foi feita uma análise pormenorizada dos espectros de UV-vis da marioria dos derivados obtidos. De forma a avaliar a potencialidade de alguns dos macrociclos sintetizados em terapia fotodinâmica (PDT), são apresentados os ensaios biológicos de PDT in vitro conduzidos com alguns dos macrociclos sintetizados. Estes ensaios envolveram a avaliação da viabilidade celular após tratamento fotodinâmico, estudos de localização celular e morfologia.

Solid contact PVC membrane electrodes based on neutral or charged carriers for the selective reading of anionic sulfamethoxazole and their application to the analysis of aquaculture water

Sulfamethoxazole (SMX) is among the antibiotics employed in aquaculture for prophylactic and therapeutic reasons. Environmental and food spread may be prevented by controlling its levels in several stages of fish farming. The present work proposes for this purpose new SMX selective electrodes for the potentiometric determination of this sulphonamide in water. The selective membranes were made of polyvinyl chloride (PVC) with tetraphenylporphyrin manganese (III) chloride or cyclodextrin-based acting as ionophores. 2-nitrophenyl octyl ether was employed as plasticizer and tetraoctylammonium, dimethyldioctadecylammonium bromide or potassium tetrakis (4-chlorophenyl) borate was used as anionic or cationic additive. The best analytical performance was reported for ISEs of tetraphenylporphyrin manganese (III) chloride with 50% mol of potassium tetrakis (4-chlorophenyl) borate compared to ionophore. Nersntian behaviour was observed from 4.0 × 10−5 to 1.0 × 10−2 mol/L (10.0 to 2500 µg/mL), and the limit of detection was 1.2 × 10−5 mol/L (3.0 µg/mL). In general, the electrodes displayed steady potentials in the pH range of 6 to 9. Emf equilibrium was reached before 15 s in all concentration levels. The electrodes revealed good discriminating ability in environmental samples. The analytical application to contaminated waters showed recoveries from 96 to 106%.

Organic field-effect transistors and phototransistors based on amorphous materials

A comparison between the charge transport properties in low molecular amorphous thin films of spiro-linked compound and their corresponding parent compound has been demonstrated. The field-effect transistor method is used for extracting physical parameters such as field-effect mobility of charge carriers, ON/OFF ratios, and stability. In addition, phototransistors have been fabricated and demonstrated for the first time by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. The active materials used in this study can be divided into three classes, namely Spiro-linked compounds (symmetrically spiro-linked compounds), the corresponding parent-compounds, and photosensitive spiro-linked compounds (asymmetrically spiro-linked com-pounds). Some of symmetrically spiro-linked compounds used in this study were 2,2',7,7'-Tetrakis-(di-phenylamino)-9,9'-spirobifluorene (Spiro-TAD),2,2',7,7'-Tetrakis-(N,N'-di-p-methylphenylamino)-9,9'-spirobifluorene (Spiro-TTB), 2,2',7,7'-Tetra-(m-tolyl-phenylamino)-9,9'-spirobifluorene (Spiro-TPD), and 2,2Ž,7,7Ž-Tetra-(N-phenyl-1-naphtylamine)-9,9Ž-spirobifluorene (Spiro alpha-NPB). Related parent compounds of the symmetrically spiro-linked compound used in this study were N,N,N',N'-Tetraphenylbenzidine (TAD), N,N,N',N'-Tetrakis(4-methylphenyl)benzidine (TTB), N,N'-Bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), and N,N'-Diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (alpha-NPB). The photosensitive asymmetrically spiro-linked compounds used in this study were 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(biphenyl-4-yl)-9,9'-spirobifluorene (Spiro-DPSP), and 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(spirobifluorene-2-yl)-9,9'-spirobifluorene (Spiro-DPSP^2). It was found that the field-effect mobilities of charge carriers in thin films of symmetrically spiro-linked compounds and their corresponding parent compounds are in the same order of magnitude (~10^-5 cm^2/Vs). However, the thin films of the parent compounds were easily crystallized after the samples have been exposed in ambient atmosphere and at room temperature for three days. In contrast, the thin films and the transistor characteristics of symmetrically spiro-linked compound did not change significantly after the samples have been stored in ambient atmosphere and at room temperature for several months. Furthermore, temperature dependence of the mobility was analyzed in two models, namely the Arrhenius model and the Gaussian Disorder model. The Arrhenius model tends to give a high value of the prefactor mobility. However, it is difficult to distinguish whether the temperature behaviors of the material under consideration follows the Arrhenius model or the Gaussian Disorder model due to the narrow accessible range of the temperatures. For the first time, phototransistors have been fabricated and demonstrated by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. Intramolecular charge transfer between a bis(diphenylamino)biphenyl unit and a sexiphenyl unit leads to an increase in charge carrier density, providing the amplification effect. The operational responsivity of better than 1 A/W can be obtained for ultraviolet light at 370 nm, making the device interesting for sensor applications. This result offers a new potential application of organic thin film phototransistors as low-light level and low-cost visible blind ultraviolet photodetectors.

Polyphenylen-Dendrimere

Polyphenylen-Dendrimere Alexander Josef Berresheim Zusammenfassung der Dissertation Die vorliegende Arbeit mit dem Thema 'Polyphenylen-Dendrimere' ist synthetisch orientiert und behandelt im Wesentlichen den Aufbau neuer Polyphenylen-Dendrimere durch die Anwendung wiederholter Diels-Alder- und Desilylierungs-Reaktionen. Diskutiert wird die Synthese der einzelnen Bausteine, die Synthese der verschiedenen Dendrimere sowie deren Charakterisierung. Außerdem wird die oxidative Cyclodehydrierung geeigneter Dendrimere zu polycyclischen aromatischen Kohlenwasserstoffen beschrieben. Die Synthese der Dendrimere beruht auf einer wiederholten Diels-Alder-Reaktion eines Tetraphenylcyclopentadienons mit einem aromatischen Acetylen. Durch die Variation des Kerns und des Verzweigungsbausteins werden die Wachstumsgrenzen, denen dieser Dendrimer-Typ unterliegt, demonstriert. Es wird gezeigt, dass ein Dendrimer, bei dessen Synthese 3,4-Di-[4-(tri-iso-propylsilylethinyl)phenyl]-2,5-diphenylcyclopentadienon als Verzweigungsbaustein verwendet wird, bis zur vierten Generation wachsen kann. Wird bei der Synthese 3,3',5,5'-Tetraethinylbiphenyl als Kern verwendet, entsteht ein Oligophenylen, das aus 302 Benzolringen besteht.Bei Dendrimeren, deren Synthese auf dem A4B-Baustein 2,3,4,5-Tetrakis-[4-(tri-iso-propylsilylethinyl)phenyl]cyclopentadienon beruht, hängt die höchste Generation, die monodispers hergestellt werden kann, von der Art des Kerns ab. Wird 1,4-Diethinylbenzol verwendet, lassen sich die ersten drei Generationen synthetisieren. Hat der Kern jedoch die Multiplizität 'vier' oder 'sechs' ist bereits bei der zweiten Generation das Ende des monodispersen Wachstums erreicht.Die Charakterisierung der Dendrimere zeigt, dass es sich um Nanopartikel mit einer stabilen Form handelt. Der Durchmesser wächst linear mit der Generation. In einem Fall war es möglich einen Einkristall zu erhalten, dessen Kristallstruktur ermittelt werden konnte. Hierbei zeigt sich, dass es zu einer hohen Einlagerung von Lösungsmitteln in der Festphase kommen kann. Dieses Ergebnis wurde auch durch gezielte Versuche zum Einlagerungsverhalten von Lösungsmitteln in der Festphase bestätigt.Der letzte Teil dieser Arbeit widmet sich der Möglichkeit, die Polyphenylen-Dendrimere zu großen zweidimensionalen Graphitausschnitten zu cyclodehydrieren. Es war generell möglich, polycyclische aromatische Kohlenwasserstoffe mit bis zu 306 Kohlenstoffatomen herzustellen. Es zeigt sich aber auch, dass mit zunehmender Größe des Aromaten, die Intensität der Nebenreaktionen zunimmt.

Structural transformations related to organic solid-state reactions: correlation studies of NMR and X-ray analysis

Eine zielgerichtete Steuerung und Durchführung von organischen Festkörperreaktionen wird unter anderem durch genaue Kenntnis von Packungseffekten ermöglicht. Im Rahmen dieser Arbeit konnte durch den kombinierten Einsatz von Einkristallröntgenanalyse und hochauf-lösender Festkörper-NMR an ausgewählten Beispielen ein tieferes Verständnis und Einblicke in die Reaktionsmechanismen von organischen Festkörperreaktionen auf molekularer Ebene gewonnen werden. So konnten bei der topotaktischen [2+2] Photodimerisierung von Zimt-säure Intermediate isoliert und strukturell charakterisiert werden. Insbesondere anhand statischer Deuteronen- und 13C-CPMAS NMR Spektren konnten eindeutig dynamische Wasserstoffbrücken nachgewiesen werden, die transient die Zentrosymmetrie des Reaktions-produkts aufheben. Ein weiterer Nachweis gelang daraufhin mittels Hochtemperatur-Röntgen-untersuchung, sodass der scheinbare Widerspruch von NMR- und Röntgenuntersuchungen gelöst werden konnte. Eine Veresterung der Zimtsäure entfernt diese Wasserstoffbrücken und erhält somit die Zentrosymmetrie des Photodimers. Weiterhin werden Ansätze zur Strukturkontrolle in Festkörpern basierend auf der molekularen Erkennung des Hydroxyl-Pyridin (OH-N) Heterosynthon in Co-Kristallen beschrieben, wobei vor allem die Stabilität des Synthons in Gegenwart funktioneller Gruppen mit Möglichkeit zu kompetetiver Wasserstoffbrückenbildung festgestellt wurde. Durch Erweiterung dieses Ansatzes wurde die molekulare Spezifität des Hydroxyl-Pyridin (OH-N) Heterosynthons bei gleichzeitiger Co-Kristallisation mit mehreren Komponenten erfolgreich aufgezeigt. Am Beispiel der Co-Kristallisation von trans--1,2-bis(4-pyridyl)ethylen (bpe) mit Resorcinol (res) in Gegenwart von trans-1,2-bis(4-pyridyl)ethan (bpet) konnten Zwischenprodukte der Fest-körperreaktionen und neuartige Polymorphe isoliert werden, wobei eine lückenlose Aufklärung des Reaktionswegs mittels Röntgenanalyse gelang. Dabei zeigte sich, dass das Templat Resorcinol aus den Zielverbindungen entfernbar ist. Ferner gelang die Durchführung einer seltenen, nicht-idealen Einkristall-Einkristall-Umlagerung von trans--1,2-bis(4-pyridyl)ethylen (bpe) mit Resorcinol (res). In allen Fällen konnten die Fragen zur Struktur und Dynamik der untersuchten Verbindungen nur durch gemeinsame Nutzung von Röntgenanalyse und NMR-Spektroskopie bei vergleichbaren Temperaturen eindeutig und umfassend geklärt werden.

Biomimetic sensor based on 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H- porphyrin iron (III) chloride and MWCNT for selective detection of 2,4-D

Exploitation of the electronic properties of carbon nanotubes for the development of voltammetric and amperometric sensors to monitor analytes of environmental relevance has increased in recent years. This work reports the development of a biomimetic sensor based on a carbon paste modified with 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron (III) chloride (a biomimetic catalyst of the P450 enzyme) and multi-wall carbon nanotubes (MWCNT), for the sensitive and selective detection of the herbicide 2,4- dichlorophenoxyacetic acid (2,4-D). The sensor was evaluated using cyclic voltammetry and amperometry, for electrochemical characterization and quantification purposes, respectively. Amperometric analyses were carried out at -100 mV vs. Ag/AgCl(KClsat), using a 0.1 mol L-1 phosphate buffer solution at pH 6.0 as the support electrolyte. Under these optimized analytical conditions, the sensor showed a linear response between 9.9 × 10-6 and 1.4 × 10-4 mol L-1, a sensitivity of 1.8 × 104 (±429) μA L mol -1, and limits of detection and quantification of 2.1 × 10 -6 and 6.8 × 10-6 mol L-1, respectively. The incorporation of functionalized MWCNT in the carbon paste resulted in a 10-fold increase in the response, compared to that of the biomimetic sensor without MWCNT. In addition, the low applied potential (-100 mV) used to obtain high sensitivity also contributed to the excellent selectivity of the proposed sensor. The viability of the application of this sensor for analysis of soil samples was confirmed by satisfactory recovery values, with a mean of 96% and RSD of 2.1% (n = 3). © 2013 Elsevier B.V.

Self-assembly of metalloporphyrins: first TPP-bipy coordination polymer with CoII (TPP=meso-tetraphenylporphyrin and bipy=4,4´-bipyridine)

Póster presentado en: 11th International Symposium on Applied Bioinorganic Chemistry. 2-5 Diciembre 2011. Barcelona, España (ISABC 2011)