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LIBRO DE RESMENES

http://sij2017unex.es/

XIV Simposio de Investigadores Jvenes (Badajoz, 2017)

BIENVENIDA

En representacin del Comit Organizador, es un autntico honor daros la bienvenida a

todos los participantes en el XIV Simposio de Investigadores Jvenes Real Sociedad

Espaola de Qumica-Sigma Aldrich (Merck), que este ao se celebrar por primera vez en

la ciudad de Badajoz entre el 7 y el 10 de noviembre de 2017.

Actualmente, el Simposio de Investigadores Jvenes es considerado como la reunin

cientfica de jvenes investigadores en el campo de la Qumica ms importante a nivel

nacional, tal y como atestiguan las trece ediciones anteriores celebradas anualmente desde el

ao 2004 con un crecimiento continuo no slo en cuanto al nmero de asistentes, sino tambin

a la calidad cientfica de los trabajos presentados. La organizacin del evento es asumida por

el Grupo Especializado de Jvenes Investigadores Qumicos (JIQ) de la Real Sociedad

Espaola de Qumica (RSEQ) y, durante su celebracin, se realiza la entrega de los premios

anuales a Jvenes Investigadores de la RSEQ-Sigma Aldrich y de SusChem-JIQ. Estos

prestigiosos galardones tienen por objeto reconocer las mejores trayectorias cientficas de

investigadores noveles y las mejores publicaciones pre- y posdoctorales del ao 2016 en

cualquier rea de la Qumica, respectivamente. Adems, como novedad, en la edicin de este

ao tambin se entregar el premio a Jvenes Investigadores RSEQ-Reaxys, dirigido a

aquellos investigadores que hayan empleado esta base de datos cientfica en la elaboracin de

sus trabajos.

El Simposio abarca todas las ramas de la Qumica moderna (Qumica Orgnica,

Qumica Inorgnica, Qumica Fsica, Qumica Analtica, Bioqumica, Qumica Mdica e

Ingeniera Qumica), englobando desde la investigacin bsica hasta las ms recientes y

novedosas aplicaciones. Por tanto, este evento constituye una oportunidad enriquecedora y

nica para los jvenes investigadores qumicos procedentes de todos los campos anteriores.

Las contribuciones cientficas se distribuirn en conferencias plenarias reservadas a los

premiados (RSEQ-Sigma Aldrich, SusChem-JIQ y RSEQ-Reaxys), comunicaciones hot topic,

comunicaciones orales, comunicaciones flash y sesiones de pster. Por otra parte, el

tradicional Taller de Empresas, una de las principales y ms reconocibles seas de identidad

del Simposio, versar en esta edicin sobre posibles salidas profesionales para los

investigadores qumicos alternativas a la trayectoria acadmica tradicional. As, se tratarn

temas como la transferencia de resultados de investigacin, la solicitud y gestin de patentes y

otras formas de proteccin de la I+D, el emprendimiento en el sector qumico o la creacin de

empresas spin off. Todo ello de una forma dinmica a travs de una mesa redonda que contar

con la participacin de expertos del Servicio de Gestin y Transferencia de Resultados de la

Investigacin de la Universidad de Extremadura, de la Junta de Extremadura y con

emprendedores responsables de la creacin de varias empresas spin off dentro del sector

qumico, los cuales nos trasladarn sus experiencias. Desde estas lneas, nos gustara

agradecer a todos los ponentes su disponibilidad y predisposicin para participar en esta

actividad.

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Este Comit Organizador se muestra enormemente satisfecho con el gran inters y

acogida que ha despertado la presente edicin del Simposio entre los jvenes investigadores

qumicos, y que se ha traducido en un elevado nmero de solicitudes de participacin. En este

sentido, hemos realizado todos los esfuerzos posibles por satisfacer esta demanda,

alcanzndose una cifra de inscritos cercana a los 150 y cubrindose de este modo la totalidad

de las solicitudes.

La ciudad de Badajoz, y con ella la Comunidad Autnoma de Extremadura, han sido

seleccionadas para acoger por primera vez una edicin de este evento cientfico de primer

nivel. Las sesiones cientficas se desarrollarn en el Saln de Grados de la Facultad de

Ciencias (edificio Juan Remn Camacho) y en el Saln de Actos del Edificio Contenedor de los

Institutos de Investigacin, ambos ubicados en el Campus de la Universidad de Extremadura

en Badajoz y a escasos metros uno del otro. Las comidas se realizarn en el saln-comedor de

la Facultad de Ciencias Econmicas y Empresariales, situado tambin en el mismo Campus de

Badajoz, mientras que la cena de gala se celebrar en el NH Gran Hotel Casino Extremadura.

Por su parte, para el alojamiento se han dispuesto dos establecimientos hoteleros, el Aparthotel

Ascarza Badajoz y el Hotel Mercure Ro Badajoz, localizados entre 5 y 10 minutos a pie del

lugar de desarrollo de las sesiones cientficas.

Y, por supuesto, como no todo iba a ser Qumica, tambin habr tiempo para el ocio y

la diversin a travs del programa social que se ha preparado. Realizaremos una visita guiada

nocturna por los principales monumentos histricos y lugares de inters de Badajoz. Pasear

por esta ciudad es sumergirse de lleno en su apasionante historia, fuertemente marcada por su

origen rabe y su carcter de plaza fronteriza en las sucesivas guerras y disputas con Portugal.

Monumentos como la Alcazaba, la de mayor extensin en toda Europa, con su imponente

Torre de Espantaperros y sus jardines de La Galera, constituyen tesoros que dan buena cuenta

de la dominacin musulmana de Batalyaws, que alcanz su mximo esplendor bajo la dinasta

aftas y el posterior imperio almohade. Otros monumentos de marcada influencia rabe son las

Casas Mudjares, primer ayuntamiento de la ciudad, y la Plaza Alta. Por su parte, el carcter

fronterizo de la ciudad ha pervivido hasta nuestros das en la extensa muralla abaluartada, con

sus mltiples puertas (de Palmas, del Pilar, de la Trinidad, etc.), el puente de Palmas y otros

elementos defensivos como el Fuerte de San Cristbal. Adems de esta visita obligada,

tambin podremos disfrutar de una cata de cervezas artesanales y del ambiente nocturno de

Badajoz.

Asimismo, desde el Comit Organizador deseamos mostrar nuestro ms sincero y

profundo agradecimiento a todas y cada una de las instituciones, tanto pblicas como privadas,

por el inters mostrado y el apoyo econmico y logstico ofrecido, sin el cual la organizacin y

celebracin de este evento cientfico hubiese sido simplemente imposible.

Como en ediciones anteriores, esperamos que el Simposio logre holgadamente sus

objetivos de que los jvenes investigadores qumicos se interrelacionen entre s, fomentando

de este modo la discusin, elemento esencial para el avance de la Ciencia y de la Qumica en

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particular, la interdisciplinariedad y el establecimiento de nuevas colaboraciones que, en un

futuro no muy lejano, esperamos vean su fruto.

Por ltimo, desde el Comit Organizador os damos una calurosa bienvenida y

deseamos que os llevis grabado en la memoria un grato e imborrable recuerdo de este XIV

Simposio de Investigadores Jvenes Real Sociedad Espaola de Qumica-Sigma Aldrich

(Merck), as como del ambiente, las gentes, las tradiciones y la gastronoma de la ciudad de

Badajoz y de toda Extremadura. Aprovechad la excelente oportunidad y disfrutad de lo mucho

que esta tierra acogedora tiene para ofreceros. Bienvenidos a nuestra casa.

Adrin Barroso Bogeat

Presidente del Comit Organizador

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COMIT CIENTFICO Jess Jimnez Barbero

Presidente de la Real Sociedad Espaola de Qumica

Emilio J. Cocinero Prez

Presidente del Grupo Especializado de Jvenes Investigadores Qumicos

Dr. Adrin Barroso Bogeat

Universidad de Cdiz y Universidad de Extremadura

Dra. Mara Victoria Gil lvarez

Dr. Emilio Viuelas Zahnos

Dra. Mara Alexandre Franco

Dra. Mara Isabel Rodrguez Cceres

Dr. Rafael Fernando Martnez Vzquez

Universidad de Extremadura

Dra. Almudena Aguinaco Martn

Dra. Ginesa Blanco Montilla

Dr. Jos Mara Pintado Caa

Universidad de Cdiz

Dra. Elena Bernalte Morgado

Metropolitan University of Manchester

COMIT ORGANIZADOR Adrin Barroso Bogeat

Mara Victoria Gil lvarez

Emilio Viuelas Zahnos

Mara del Pilar Romero Fernndez

Almudena Prez Pereira

Elsabet Martn Tornero

Vernica Luque Agudo

Mnica Palomino Vasco

Silvia Gutirrez Tarrio

Sara Martillanes Costumero

Olga Monago Maraa

Manuel Cabrera Baegil

Selena Carretero Pea

Felipe Martn Vegas

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PATROCINADORES

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EDICIONES ANTERIORES

I Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2004, Madrid

II Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2005, Ciudad Real

III Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2006, Tarragona

IV Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2007, Burgos

V Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2008, Santiago de Compostela

VI Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2009, Granada

VII Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2010, Valencia

VIII Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2011, Torremolinos

IX Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2012, Zaragoza

X Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2013, Madrid

XI Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2014, Bilbao

XII Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2015, Barcelona

XIII Simposio de Investigadores Jvenes RSEQ-Sigma Aldrich

2016, Logroo

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PROGRAMA

Hora MARTES 7/XI/2017 Hora MIRCOLES 8/XI/2017

9:00 Marek Grzelczak (Premio RSEQ)

9:30 Hot topic 2: Vernica Luque Agudo

9:50 Oral 5: Ester Jimnez Moreno

10:05 Oral 6: Manuel Cabrera Baegil

10:20 Oral 7: M Iris Martn Garca

10:35 Oral 8: Carmen Rodrguez Maldonado

10:50 Flash oral 1: Alesandere Ortega Altonaga

11:00 Pausa caf. Sesin de psteres

11:30 Mestrelab (Esther Vaz)

11:45 Oral 9: Javier Carreras Prez-Aradros

12:00 Oral 10: Lled Bou Iserte

12:15 Oral 11: Jorge Humbras Martn

12:30 Oral 12: Emilio J. Cocinero Prez

12:45 Flash oral 2: Susn Azpeitia Coscarn

12:55 Flash oral 3: Carlos Bentez Martn

13:05 Flash oral 4: Andoni Zabala Lekuona

13:15 Presidencia JIQ (Emilio J. Cocinero)

13:30 Registro y colocacin de psters 13:30 Comida

15:30 Acto de apertura y entrega de premios 15:30 Manuel Moliner (Premio RSEQ)

16:00 Jess Campos (Premio RSEQ) 16:00 Hot topic 3: Jos Miguel Gonzlez

Domnguez

16:30 Hot topic 1: Antonio M. Rguez. Garca 16:20 Oral 13: Olatz Olaizola Aizpuru

16:50 Pausa 16:35 Oral 14: Viviana Jehov Gonzlez Velzquez

17:00 Bienvenida autoridades 16:50 Flash oral 5: Cintia Virumbrales Ortiz

17:30 Pausa caf. Sesin de psteres 17:00 Pausa caf. Sesin de psteres

18:00 Oral 1: Ana Torres Martnez 17:30 Premio Reaxys

18:15 Oral 2: Alba Collado Martnez 18:00 Oral 15: Joseba Izquierdo Arruferia

18:30 Oral 3: Diego Cortizo Lacalle 18:15 Oral 16: Mara Cerrato lvarez

18:45 Oral 4: Luis A. Trujillo Cayado 18:30 Oral 17: Pascual Oa Burgos

20:00 Visita guiada, recepcin y aperitivo 18:45 Oral 18: Daniel Gonzlez Muoz

19:00 Flash oral 6: Carla Arnau del Valle

19:10 Flash oral 7: Diego Ros guez

19:20 Flash oral 8: Edgar Maci Gil

20:00 Cata de cervezas artesanales

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Hora JUEVES 9/XI/2017 Hora VIERNES 10/XI/2017

9:00 Anna Company (Premio RSEQ) 9:00 Liher Prieto (Premio SusChem Predoc)

9:30 Hot topic 4: Premio Reaxys 9:30 Hot topic 5: Sergio Rojas Buzo

9:50 Oral 19: Leyre Marzo Puerta 9:50 Oral 27: Mikiko Vzquez Nakagawa

10:05 Oral 20: Juan Vicente Alegre Requena 10:05 Oral 28: Rafael Carlos Gonzlez Cano

10:20 Oral 21: M Eugenia Prez Ojeda 10:20 Oral 29: Jos Miguel Mateo Gonzlez

10:35 Oral 22: Eva M Gallego Snchez 10:35 Oral 30: Marine Reynaud

10:50 Flash oral 9: Felipe de la Cruz Martnez 10:50 Flash oral 13: Ral Martn Lozano

11:00 Pausa caf. Sesin de psteres 11:00 Pausa caf. Sesin de psteres

11:30 Merck (Manuela Vacatello) 11:30 Oral 31: Juan Garca de la Concepcin

11:45 Oral 23: Macarena Martnez Bailn 11:45 Oral 32: Mara Jos Martn Piero

12:00 Oral 24: Endika Martn Encinas 12:00 Oral 33: Yago Garca-Rodeja Navarro

12:15 Oral 25: M Jess Cabrera Afonso 12:15 Oral 34: Silvia Cabrera Herranz

12:30 Oral 26: Jos Navarro Snchez 12:30 Flash oral 14: Sandra Daz Cabrera

12:45 Flash oral 10: Ftima Morales Marn 12:40 Flash oral 15: Elsabet Martn Tornero

13:00 Flash oral 11: Francisco Ortega

Higueruelo 12:50 Flash oral 16: Xabier del Corte

13:05 Flash oral 12: Manuel Salgado Ramos 13:00 Acto de clausura

13:15 Reaxys

13:30 Comida

15:30 Mara Escudero (Premio SusChem

Posdoc)

16:00 Taller de empresas y mesa redonda

17:30 Pausa caf. Sesin de psteres

18:00 Conferencia divulgacin

18:30 Junta JIQ

21:00 Cena de gala

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XIV SIMPOSIO DE INVESTIGADORES JVENES DE LA RSEQ

Libro de Resmenes

Comit Organizador

Adrin Barroso Bogeat

[email protected]

Mara Victoria Gil lvarez

[email protected]

Emilio Viuelas Zahnos

[email protected]

http://sij2017unex.es

ISBN: 978-84-697-7162-4

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PREMIADOS

RSEQ


Jess Campos studied Chemistry at University of Sevilla

receiving the First National Award in 2007. He moved to the

University of Manchester to work under the guidance of Prof.

John D. Sutherland (MPhil, 2008). Back to Spain he joined the

group of Prof. Ernesto Carmona to work on fundamental

organometallic chemistry and receiving two PhD Extraordinary

Awards and an International PhD Distinction (2012) after

spending a visiting stay with Prof. Maurice Brookhart

(University of North Carolina, USA, 2010).

He returned to the USA as a postdoctoral researcher joining the prestigious group of Prof.

Robert H. Crabtree at Yale University to work in green catalysis and energy-related

transformations (2013-2014). He was awarded with a Talentia Postdoc Fellowship for a second

postdoctoral period in the laboratories of Prof. Simon Aldridge at University of Oxford to focus

on bond activation and catalysis with main group systems (2014-2016).

In 2016 he moved back to the University of Sevilla after securing a Marie Curie IF fellowship

and one year later he was awarded with a permanent position as Research Scientist of the

Spanish National Research Council (CSIC) to develop his independent career at the Institute of

Chemical Research (IIQ) at Sevilla. More recently, he was granted an ERC Starting Grant

project from the European Research Council to develop new cooperative catalysts from a

multidisciplinary approach.

Dr. Campos is author of more than 45 scientific articles in international top journals and his

research has been recognized with several research prizes such as a project for Young

Researchers from the BBVA Foundation, Javier Benjumea Puigcerver Research Prize (shared

with Prof. Carmona) or the Young Researchers Real Maestranza de Caballera de Sevilla

Award. His interests include all aspects of inorganic and organometallic chemistry, with

particular emphasis on cooperative chemistry and the development of new catalytic reactions.

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ORO Y FOSFINAS DE TERFENILO, DE LA INTERACCIN A LA

FRUSTRACIN

Jess Campos

Instituto de Investigaciones Qumicas (IIQ) and Departamento de Qumica Inorgnica, CSIC

and Universidad de Sevilla, Avda. Amrico Vespucio 49, 41092 Sevilla (Spain)

Los ligandos fosfina se encuentran en una posicin privilegiada dentro de la qumica

organometlica y la catlisis homognea, en gran medida debido a la posibilidad de modular de

manera sencilla sus propiedades estricas y electrnicas. En particular, el uso de fosfinas

voluminosas ha sido crucial en el desarrollo de nuevos procesos catalticos [1] y ha permitido

caracterizar numerosos complejos organometlicos altamente reactivos por estabilizacin

cintica [2]. Las fosfinas de biarilo (PR2Ar, Ar = bifenilo) desarrolladas por Buchwald son un

ejemplo paradigmtico [3], sin embargo, apenas existe informacin sobre sus anlogas de

terfenilo (2,6-C6H3-Ar2), a pesar de la excepcional capacidad estabilizadora de este fragmento

[4]. Es por ello que en los ltimos aos decidimos preparar una amplia familia de estos ligandos

y sus correspondientes complejos con metales preciosos, particularmente oro, platino, iridio y

rodio [5a]. Los estudios de reactividad de estas especies nos han permitido aislar estructuras

sin precedentes [5b] e identificar modos de reaccin altamente inusuales. Asimismo,

combinando el carcter cido de estos complejos voluminosos de oro con el comportamiento

bsico de especies de platino (0) hemos desarrollado el primer par de Lewis frustrado basado

nicamente en metales de transicin [5c].

Referencias

[1] Ver por ejemplo: a) W. Xiao-Feng, F. Xianjie, W. Lipeng, R. Jackstell, H. Neumann, M. Beller, Accounts of ChemicalResearch, 2014, 47, 1041; b) A. F. Littke, G. C. Fu, Angewandte Chemie, International Edition, 2002, 41, 4176; c) J.Hartwig, Accounts of Chemical Research, 2008, 41, (2008), 1534.

[2] Ver por ejemplo: a) W. H. Bernskoetter, C. K. Schauer, K. I. Goldberg, M. Brookhart, Science, 2009, 326, 553; b) F.Schaper, S. R. Foley, R. F. Jordan, Journal of the American Chemical Society, 2004, 126, 2114; c) J. Campos, R.Peloso, E. Carmona, Angewandte Chemie, International Edition, 2012, 51, 8255.

[3] a) J. P. Wolfe, S. Wagaw, J.-F. Marcoux, S. L. Buchwald, Accounts of Chemical Research, 1998, 31, 805; b) R.Martin, S. L. Buchwald, Accounts of Chemical Research, 2008, 41, 1461.

[4] T. Nguyen, A. D. Sutton, M. Brynda, J. C. Fettinger, G. J. Long, P. P. Power, Science, 2005, 310, 844.

[5] a) L. Ortega-Moreno, M. Fernndez-Espada, J. J. Moreno, C. Navarro, J. Campos, S. Conejero, J. Lpez-Serrano,C. Maya, R. Peloso, E. Carmona, Polyhedron, 2016, 116, 170; b) M. F. Espada, J. Campos, J. Lpez-Serrano, M. L.Poveda, E. Carmona, Angewandte Chemie, International Edition, 2015, 54, 5379; c) J. Campos, Journal of theAmerican Chemical Society, 2017, 139, 2944.

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Marek Grzelczak naci en Gostyn (Polonia) en 1980 y estudi

Ciencias Qumicas en la Universidad Adam Mickiewicz en

Poznan (2004). Realiz la tesis doctoral (Premio

Extraordinario) en la Universidad de Vigo (2008) bajo la

supervisin del profesor Luis M. Liz-Marzn.

De 2008 hasta 2012 realiz dos estancias postdoctorales, la

primera de ellas con el profesor Maurizio Prato (Universidad de

Trieste), en la cual centr su investigacin en el uso de

nanotubos de carbono para aplicaciones en fotocatlisis.

Despus se traslad al Instituto Max-Planck para realizar su segunda estancia postdoctoral con

el profesor Markus Antonietti, investigando la oxidacin de agua en el contexto de la

fotosntesis artificial.

En 2012 vuelve a la Universidad de Vigo con una beca Juan de la Cierva y posteriormente, se

traslada al Centro de Investigacin Cooperativa en Biomateriales en San Sebastin como

investigador Ikerbasque, donde centra su actividad cientfica en el uso de nanopartculas

metlicas en el campo de la fotoqumica y el diseo de biosensores.

En actualidad trabaja en Donostia International Physics Center (San Sebastin) como

Ikerbasque Research Associate donde desarrolla su lnea de investigacin independiente. Su

carrera investigadora ha dado lugar a la publicacin de 60 artculos en revistas internacionales

de alto impacto.

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APPLICATION OF PLASMONIC NANOPARTICLES IN SELF-ASSEMBLY

AND ALL-METAL PHOTOCHEMISTRY

Marek Grzelczak1,2

1Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, Donostia San

Sebastin, 20018 (Spain); 2Ikerbasque, Basque Foundation for Science, 48013 Bilbao (Spain).

[email protected]

Tremendous progress over the past decades has been made in the synthesis of metallic

nanocrystals that emerged a library of particles with precisely controlled sizes, shapes, and

surface chemistry [1,2]. Today, the particles serve as building blocks for hierarchical self-

assembly and as active species in a variety of catalytic transformations. In the first part of the

talk, we will exploit hydrophobic forces to self-organize plasmonic nanoparticles into discrete

clusters of different sizes with well-controlled interparticle distances [3,4]. The second part of the

talk will be devoted to all-metal photochemistry, a field of research dealing with the use of

plasmonic nanoparticles in light-assisted chemical transformations [5]. We will define

geometrical and structural constraints in design of efficient photocatalyst to regenerate cofactor

molecules.

References

[1] M. Grzelczak, J. Prez-Juste, P. Mulvaney, L. M. Liz-Marzn, Chemical Society Reviews, 2008, 37, 1783.

[2] L. M. Liz-Marzn, M. Grzelczak, Science, 2017, 356, 1120.

[3] A. Snchez-Iglesias, M. Grzelczak, T. Altantzis, B. Goris, J. Prez-Juste, S. Bals, G. Van Tendeloo, S. H.Donaldson, B. F. Chmelka, J. N. Israelachvili, L. M. Liz-Marzn, ACS Nano, 2012, 6, 11059.

[4] M. Grzelczak, A. Snchez-Iglesias, H. H. Mezerji, S. Bals, J. Prez-Juste, L. M. Liz-Marzn, Nano Letters, 2012, 12,4380.

[5] A. Snchez-Iglesias, J. Barroso, D. Martinez-Solis, J. M. Taboada-Varela, F. Obelleiro-Basteiro, V. Pavlov, A.Chuvilin, M. Grzelczak, Journal of Materials Chemistry A, 2016, 4, 7045.

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mailto:[email protected]


Manuel Moliner completed his Ph.D. at the Polytechnic

University of Valencia (UPV), in Chemistry, under the guidance

of Prof. Avelino Corma and Dr. Maria J. Daz in 2008. His thesis

work involved the synthesis of new zeolitic structures by using

high-throughput methodologies.

Afterward, he completed a two-year postdoc (2008-2010) with

Prof. Mark Davis at the California Institute of Technology

(Caltech), working on the design and synthesis of functional

materials with application in different catalytic processes, mainly

in biomass transformations.

He joined the Instituto de Tecnologa Qumica (ITQ) as a Ramn y Cajal researcher in 2011,

and since 2014, he is a Tenured Scientist of the Spanish National Research Council (CSIC). His

research lies at the interface of heterogeneous catalysis and materials design, focusing on the

molecular-level preparation of selective materials for their use as efficient catalysts in

industrially-relevant chemical processes.

Manuel Moliner has published 68 papers in international journals, and is co-inventor of 25

international patents (11 transferred to industry and 4 presented jointly with industry). He has 45

contributions to international conferences and national congresses, and he has been invited in

16 occasions to deliver conferences and seminars (including 2 plenary and 6 keynote lectures).

Manuel has received different national and international awards, as the EFCATS Thesis

Award to the best Ph.D. Thesis in Europe during 2007-2009, the TR-35 Spain 2011 awarded

by MIT to young talents in Spain under-35, the FISOCAT 2014 to young scientists under 40 in

Latin America, or the RSEQ-Young researcher awarded by the Spanish Royal Society of

Chemistry (RSEQ) in 2017.

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CONTROL DE LA ARQUITECTURA EN LA ESCALA NANOMTRICA:

SNTESIS RACIONAL Y APLICACIONES CATALTICAS

Manuel Moliner

Instituto de Tecnologa Qumica, Universitat Politcnica de Valncia-Consejo Superior de

Investigaciones Cientficas, Avenida de los Naranjos s/n, 46022 Valncia, Espaa.

[email protected]

Las zeolitas son xidos cristalinos microporosos con poros y cavidades bien definidos de

dimensiones moleculares (~3-12 ), y que presentan amplia aplicacin en adsorcin de gases,

intercambio catinico o catlisis, entre otras aplicaciones [1]. El uso de agentes directores de

estructura orgnicos (ADEO) e inorgnicos (ADEI) durante su sntesis, permite controlar el

tamao de sus poros y cavidades, su composicin qumica y/o su tamao de cristal, abriendo

nuevas oportunidades para su aplicacin como catalizadores en procesos qumicos de gran

inters industrial.

En este sentido, se presentarn distintas estrategias de sntesis desarrolladas recientemente

con el objetivo mltiple de mejorar la eficiencia de su preparacin (costes o rendimientos de

sntesis), su actividad cataltica, o su resistencia frente a procesos de desactivacin. Primero,

se presentar el uso combinado de complejos organometllicos con otras molculas orgnicas

como ADEOs cooperativos, permitiendo la obtencin de zeolitas de poro pequeo conteniendo

metales aislados como catalizadores activos y altamente estables para la reduccin cataltica

selectiva de NOx (ver Figura 1a) [2]. En segundo lugar, se mostrar la sntesis de distintas

zeolitas nanocristalinas con tamaos de partcula menores de 50 nm utilizando ADEOs de

naturaleza no-surfactante y/o fuentes de silicio pre-cristalizadas como ADEI, as como su

aplicacin como catalizadores eficientes para los procesos metanol-a-olefinas (MTO) u

oligomerizacin de olefinas a combustibles lquidos (ver Figura 1b) [3]. Finalmente, se mostrar

el uso novedoso de ADEOs que mimetizan los estados de transicin de reacciones

preestablecidas, con el fin de generar cavidades especficas que alberguen los estados de

transicin, mejorando la actividad cataltica y la selectividad hacia los productos deseados (ver

Figura 1c) [4].

Figura 1: (A) Co-ADEOs para la sntesis eficiente de metal-zeolitas, (B) ADEOs utilizados para la preparacin de

catalizadores nanocristalinos, y (C) ADEOs mmicos de estados de transicin de reacciones de inters industrial.

Referencias

[1] J. Cejka et al., Catalysis Today, 2012, 179, 2.

[2] a) R. Martnez-Franco et al., ChemCatChem, 2013, 5, 3316; b) N. Martn et al., Chemical Communications, 2015,51, 9965; c) N. Martn et al., Applied Catalysis B, 2017, 217,125.

[3] a) N. Martn et al., Chemical Communications, 2016, 52, 6072; b) R. Martnez-Franco et al., Chemical Science,2016, 7,102; c) R. Daz-Rey et al., ACS Catalysis, 2017, 7, 6170.

[4] Gallego et al., Science, 2017, 355,1051.

(A) (B) (C)

17


Anna Company studied Chemistry at the University of Girona

(Spain, 2000 - 2004) and she obtained her PhD in Chemistry in

December 2008 at the same university under the supervision of

Dr. Miquel Costas. The main focus of her PhD thesis was the

activation of O2 at copper and iron-based bioinspired

complexes. During her doctoral studies, she performed two

short research stays in highly recognized research groups. In

2006, she spent 3 months in the University of Minnesota

(Minneapolis, USA) under the supervision of Prof. Dr.

Lawrence Que Jr. and in 2007 she visited the laboratories of

Prof. Dr. Karl Wieghardt in the Max Planck Institut fr Bioanorganische Chemie (Mlheim an der

Ruhr, Germany).

In April 2009 she joined the group of Prof. Dr. Driess at the Technische Universitt Berlin

(Germany) as a postdoctoral researcher. Her postdoctoral position was funded by the European

Commission by a 2-year Marie Curie Intra-European Fellowship. Her work was focused on the

study of the mechanisms of O2 activation at nickel centers and the study of the reactivity of the

resulting nickel-dioxygen adducts. Noteworthy, during this period, she won the 2010 Dalton

Young Researchers Award, awarded by the Royal Society of Chemistry to a young European

inorganic chemist.

After the two-year stay in Berlin, in April 2011 she returned to the University of Girona, firstly as

a postdoctoral associate and she was appointed as a Ramn y Cajal researcher (2012-2016).

During this period, she started her independent research line thanks to the funding from a

Career Integration Grant from the European Commission. Since then, she has directed two PhD

theses (Dr. J. Serrano-Plana, July 2016 and Dr. T. Corona, February 2017) and 7 master

theses. Together with Dr. X. Ribas she has been granted with two research projects from the

Spanish Ministry of Science in 2013 and 2016. Since January 2017 Anna is appointed as

Research Director.

Her background on activation of small molecules and oxidation chemistry with first-row transition

metals acquired during her PhD and postdoctoral experiences sets the basis for the research

topics she is currently working on. She works on the activation of small molecules such as N2O

or O2 and on the detection and characterization of high valent metal-oxygen and metal-nitrogen

species with relevance in catalysis.

Annas work has been published in 52 articles in peer reviewed journals which have received

over 1400 citations and her h-index is 21. Moreover, she has published 5 book chapters and 5

Spanish patents. She has delivered 13 lectures at international conferences (5 of them invited)

and at universities or research centers (9 contributions). Anna received the 2015 Clara

Immerwahr Award, a prize given annually by the Cluster of Excellence UniCat in Germany, and

the Premio RSEQ Lilly Joven Investigador 2016, awarded every year to a young researcher by

the Spanish Royal Society of Chemistry and the chemical company Eli Lilly.

18


SPECTROSCOPIC STUDIES AND OXIDIZING REACTIVITY OF TWO HIGH-

VALENT Ni-OXYGEN SPECIES

Teresa Corona,1 Apparao Draksharapu,

2 Sandeep K. Padamati,

2 Florian Felix Pfaff,

3 Ferran

Acua-Pares,1 Vlad-Martin Diaconescu,

1 Julio Lloret-Fillol,

4 Kallol Ray,

3 Wesley R. Brown,

2

Anna Company1

1Grup de Qumica Bioinorgnica Supramolecular i Catlisi (QBIS-CAT), IQCC, Universitat de

Girona (Catalonia - Spain). 2University of Groningen (The Netherlands).

3Humboldt Universitt

zu Berlin (Germany). 4Institut Catal dInvestigaci Qumica, Tarragona (Catalonia Spain).

[email protected]

The study of high-valent nickel complexes has attracted the attention of the bioinorganic

chemistry community to provide models of nickel-containing enzymes that catalyze redox

processes. Moreover, high-valent nickel-oxygen species have been frequently postulated as

key reaction intermediates in the catalytic cycle of oxidation reactions. However, only a handful

of such species have been properly trapped and characterized. Only very recently

spectroscopic description and reactivity investigations on well-defined nickel(III)-oxygen species

have been reported [1-3].

Herein, we describe the preparation of two highly reactive high-valent nickel-oxygen

intermediates nickel-oxyl (2) and nickel-OCl (3) that have been spectroscopically trapped by

low-temperature reaction of 1 with mCPBA (meta-chloroperbenzoic acid) and NaOCl

respectively (see Figure 1) [4,5]. Both compounds could be characterized by means of several

spectroscopic (UV-vis, EPR, rRaman, XAS, ESI-MS) and computational methods. Moreover,

these species were able to oxidize organic substrates including C-H bonds, C-C double bonds

and sulfides.

Compounds 2 and 3 are more reactive towards organic substrates than the previously reported

well-defined Ni-oxygen species. Most probably, the use of a dianionic ligand structure promotes

the formation of these well-defined high-valent nickel-oxygen species that are otherwise highly

elusive.

Results disclosed here demonstrate the viability of high-valent nickel-oxygen species in

oxidation reactions and their potential use as catalysts in such processes. Further works in this

direction are needed to get deeper insight into this chemistry, which until now has been poorly

developed compared to other transition metals such as manganese, iron or copper.

Figure 1. Representation of the nickel species formed upon reaction of 1 with mCPBA or NaOCl.

References

[1] P. J. Donoghue, J. Tehranchi, C. J. Cramer, R. Sarangi, E. I. Solomon, W. B. Tolman, Journal of the AmericanChemical Society, 2011, 133, 17602.

[2] F. F. Pfaff, F. Heims, S. Kundu, S. Mebs, K. Ray, Chemical Communications, 2012, 48, 3730.

[3] P. Priovano, E. R. Farquhar, M. Swart, A. J. Fitzpatrick, G. G. Morgan, A. R. McDonald, Chemistry - A EuropeanJournal, 2015, 21, 3785.

[4] T. Corona, F. Pfaff, F. Acua-Pars, A. Draksharapu, C. J. Whiteoak, V. Martin-Diaconescu, J. Lloret-Fillol, W. R.Browne, K. Ray, A. Company, Chemistry - A European Journal, 2015, 21, 15029.

[5] T. Corona, A. Draksharapu, S. K. Padamati, I. Gamba, V. Martin-Diaconescu, F. Acua-Pars, W. R. Browne, A.Company, Journal of the American Chemical Society, 2016, 138, 12987.

19

PREMIADOS

SusChem


Liher Prieto graduated in Chemistry in the year 2012 for the

University of the Basque Country (UPV/EHU), carrying a year of

study as an Erasmus student developing a research project

related to the Design and Synthesis of Novel AMPA-Receptor

Modulators as potential drugs for treatment of Alzheimers

disease under de supervision of Prof. Craig Jamieson in the

University of Strathclyde (Glasgow, UK).

These studies were followed by the Master degree developing a

project on the use of non-conjugated dienals as trienamine

precursors and their reactivity toward enantioselective Diels-Alder processes under de

supervision of Prof. Jos L. Vicario in the University of the Basque Country.

PhD studies were developed in the same research group focusing on the development of

Unconventional Reactivity Patterns in Asymmetric Organocatalytic Cycloaddition Reactions,

making use of chiral organocatalyst to trigger unexpected reactivity. During this period, he

carried out a stay in The Scripps Research Institute (La Jolla, CA) in Prof. Phil S. Barans

laboratories working on the study of strain-release driven reactivity of small polycyclic molecules

conducting to the discovery of the Strain Release Amination reaction.

Liher obtained his PhD degree in 2017, and he currently works as a postdoctoral fellow in Prof.

Vicarios research group.

21


STRAIN-RELEASE AMINATION

Liher Prieto,1 Phil S. Baran

2

1Departament of Organic Chemistry II, Faculty of Science and Technology, University of the

Basque Country (UPV/EHU), P.O. Box 644, 48080 Bilbao, Spain; 2Departament of Chemistry,

The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA. [email protected]

Research in modern medicinal chemistry deeply relies on the discovery of new synthetic methods and applications to access bioisosteres [1] as a vital strategy to overcome difficulties related to design and development of drug candidates [2]. Among the most useful bioisosteres, strained ring systems have been traditionally considered as elusive motifs due to their sparse presence in nature and the challenges that represents their synthesis [3].

In this context, it was envisioned that the ring-strain release could be used as the driving force to achieve unprecedented synthetic transformations leading to the synthesis of the aforementioned valuable bioisosteres.

The implementation of this concept motivated the discovery of a new methodology which implied the use of small strained bicyclic rings, such as [1.1.1]propellane, 1-azabicyclo[1.1.0]butane and 1-(arylsulfonyl)bicyclo[1.1.0]butane (Scheme 1). These substrates presented noteworthy propensity to experience reactions with amine nucleophiles, in a transformation that resembles hydroamination reaction and led to the formation of products of great interest for pharmaceutical industry, since the reaction is a powerful synthetic tool for any-stage funtionalization of amine compounds [4], along with other heteronucleophilic species [5].

Scheme 1

The reaction represents a novel strategy for the late functionalization of pharmaceutically interesting compounds, giving access to previously evasive bioisosteric forms, while retrieving known but underexploited reactivity of polycyclic strained molecules.

References

[1] H. Erlenmeyer, E. Berger, Biochemische Zeitschrift, 1932, 252, 22.

[2] N. A. Meanwell, Journal of Medicinal Chemistry, 2011, 54, 2529.

[3] M. V. Westphal, B. T. Wolfstdter, J. M. Plancher, J. Gatfield, E. M. Carreira, ChemMedChem, 2015, 10, 461.

[4] R. Gianatassio, J.M. Lopchuk, J. Wang, C.-M Pan, L. R. Malins, L. Prieto, T. A. Brandt, M. R. Collins, G. M. Gallego,N. W. Sach, J. E. Spangler, H. Zhu, J. Zhu, P. S. Baran, Science, 2016, 351, 241.

[5] J. M. Lopchuk, K. Fjelbye, Y. Kawamata, L. R. Malins, C.-M. Pan, R. Gianatassio, J. Wang, L. Prieto, J. Bradow, T.A. Brandt, M. R. Collins, J. Elleraas, J. Ewanicki, W Farrell, O. O. Fadeyi, G. M. Gallego, J. J. Moussea, R. Oliver, N. W.Sach, J. K. Smith, J. E. Spangler, H. Zhu, J. Zhu, P. S. Baran, Journal of the American Chemical Society, 2017, 139,3209.

22


Mara Escudero Escribano (Cceres, 1983) was

undergraduate at the UEx, where she studied Chemical

Engineering (awarded Outstanding student as best academic

record of her promotion). In 2011, she obtained her PhD in

Chemistry from the UAM. Her PhD was awarded with the best

PhD in Chemistry in the region of Madrid 2012 by the RSEQ

(2012), the Pedro Sanchez Award for the best PhD Thesis

related to Hydrogen Energy and Fuel Cells by the AeH2 and

PTE-HPC, and Extraordinary PhD Award 2012 by the UAM.

She started her postdoct research at the Technical University of Denmark in 2012. She

investigated novel electrocatalysts and achieved her biggest success with her systematic study

of the trends in oxygen reduction amongst platinum-lanthanide alloys. She found that, by tuning

the lanthanide contraction, the catalytic properties could be controlled. This work was published

in Science (2016). In 2014, she was awarded the Sapere Aude: Research Talent Grant, from

the Danish Council for Independent Research. Thanks to this grant, she spent two years (2015-

2017) at the Department of Chemical Engineering at Stanford University.

In 2015, Mara was nominated by the Danish National Research Foundation to join

AcademiaNet, Expert Database for Outstanding Female Academics, and she is a member since

then. In 2016, Maria was awarded the European Young Chemist Award 2016-Gold Medal

(EuCheMS), awarded to a European researcher under 35 whose research in chemistry displays

high level of excellence and distinction. In 2017, Mara has been awarded CIDETEC Award

2016 in the category of Young Researchers in Electrochemistry by the Electrochemistry Group

of the RSEQ and the SusChem Young Chemistry Researcher Award in the Postdoc category by

the Spanish Technology Platform for Sustainable Chemistry. Moreover, she has been awarded

the prestigious Griess Lectureship 2017 by the RSC.

Since March 2017, Mara has a tenure-track assistant professorship position at the Nano-

Science Centre and the Department of Chemistry at the University of Copenhagen, where she

leads the Nano-Electrochemistry Group. Her research is focused on conducting model studies

on well-defined surfaces and tailoring electrochemical interfaces for sustainable energy and

synthesis of valuable chemicals. She has combined electrochemical methods with in situ

spectroscopy, electrochemical scanning tunneling microscopy and in situ/operando synchrotron

X-ray based techniques. She is author of 22 papers published in high impact factor journals,

including Science, Nature Chem., Nature Mat. and J. Am. Chem. Soc. Her publications

accumulate more than 600 citations (Researcher ID: D-1408-2011). In addition, she is co-

inventor of three patents. She has presented her work at several international conferences,

including an invited keynote lecture and seven invited talks, as well as at invited seminars at

universities including Stanford University, Massachusetts Institute of Technology, and the

University of California, Berkeley.

23


TUNING THE ACTIVITY OF PT ALLOY ELECTROCATALYSTS BY MEANS

OF THE LANTHANIDE CONTRACTION

Mara Escudero Escribano

Departament of Chemistry, University of Copenhagen, Universitetsparken 5, 2100,

Copenhagen, Denmark. [email protected]

Polymer electrolyte membrane fuel cells are expected to play a key role in a future society

based on sustainable energy. However, the high loadings of Pt required to compensate for the

slow kinetics of the oxygen reduction reaction (ORR) constitute a major obstacle for a

commercially competitive reality. In order to improve the reaction kinetics and reduce the Pt

loading at the fuel cell cathode, where the ORR takes place, we need to develop more efficient

electrocatalysts. Researchers have intensively studied alloys of Pt with late transition metals for

the ORR. However, these alloys typically degrade by dealloying under fuel cell conditions, due

to dealloying. In contrast, alloys of Pt and lanthanides present exceptionally negative alloying

energy, which should increase their resistance to degradation.

We discovered that some platinum-lanthanide alloys such as platinum-gadolinium are very

active and stable ORR electrocatalysts [1,2]. The active phase consists of a compressed Pt

overlayer formed by acid leaching [1-3].

In order to study the trends in ORR

activity for different levels of

compression, we systematically studied

eight novel Pt-lanthanide and Pt-alkaline

earth polycrystalline electrodes, Pt5M,

where M is lanthanum, cerium,

samarium, gadolinium, terbium,

dysprosium, thulium, or calcium [1].

These materials are amongst the most

active Pt-based catalysts ever reported,

presenting up to a 3 to 6-fold increase in

ORR activity, relative to Pt. Notably, the

experimental ORR activity versus the

lattice parameter from X-ray diffraction

follows a volcano relation (Fig. 1). We

have used the lanthanide contraction to

control strain effects and tailor the

activity, stability and reactivity of Pt alloys

[1].

Fig. 1. Activity-lattice parameter volcano.

References

[1] M. Escudero-Escribano et al., Science, 2016, 352, 73.

[2] M. Escudero-Escribano et al., Journal of the American Chemical Society, 2012, 134, 16476.

[3] A.F. Pedersen et al., Nano Energy, 2016, 29, 249.

24

COMUNICACIONES

Hot Topic


FIRST-PRINCIPLES STUDY ON THE MICROSOLVATATION OF MELAMINE

ON GRAPHENE

Antonio M. Rodrguez,1,2

Ana B. Muoz-Garca,1 Orlando Crescenzi,

1

Ester Vzquez,2,3

Michele Pavone 1

1Dipartimento di Scienze Chimiche, Universit degli Studi di Napoli Federico II, Via Cinthia,

Naples, Italia. 2Instituto Regional de Investigacin Cientfica Aplicada (IRICA), Universidad de

Castilla-La Mancha, 13071 Ciudad Real, Spain. 3Facultad de Ciencias y Tecnologas Qumicas,

Universidad de Castilla-La Mancha, Avda. Camilo Jos Cela S/N, 13071, Ciudad Real, Spain.

First isolated in 2004, [1] graphene has sparked a great scientific interest thanks to its peculiar mechanical and electronic properties, which promise to upgrade many technologies, from microelectronics to biosensing and nano-medicine [2]. These potential applications require stable graphene dispersions with a good balance between yield and ease of manipulation, where graphene electronic properties are retained. Exfoliation of graphite via non-covalent intercalation of small aromatic molecules [3] represents a promising strategy to obtain high quality graphene while avoiding chemical modifications that can compromise its electronic features.

Among the many molecules that have been proposed as exfoliating agents, only a few successfully exfoliate and stabilize graphene in aqueous media: one example is 2,4,6-triamino-1,3,5-triazine, also known as melamine [3]. In order to explain the role of melamine on stable graphene aqueous dispersions, we have studied the nature of water-melamine-graphene interactions with state-of-the-art density functional theory (DFT) calculations. We analysed different melamine, water and melamine/water coverages and symmetries on graphene within a super-cell slab periodic approach. From our results, we propose a microsolvation model where the subtle interplay between non-covalent interactions, namely dispersion and hydrogen-bonding, provides the necessary thermodynamic driving force to stabilize the graphene-water system with small amounts of melamine [4]. The results discussed in this contribution provide useful insights for the rational design of new non-toxic molecules that can conveniently adsorb with water on graphene, thus enabling its effective use in aqueous media.

References

[1] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, A. A. Firsov,Science, 2004, 306, 666.

[2] a) K. S. Novoselov, V. I. Fal'ko, L. Colombo, P. R. Gellert, M. G. Schwab, K. Kim, Nature, 2012, 490, 192; b) V.Palermo, Chemical Communications, 2013, 49, 2848.

[3] V. Leon, A. M. Rodriguez, P. Prieto, M. Prato, E. Vazquez, ACS Nano, 2014, 8, 563.

[4] A. M. Rodrguez, A. B. Muoz-Garca, O. Crescenzi, E. Vzquez, M. Pavone Physical Chemistry Chemical Physics,

2016, 18, 22203.

26


ON WATER: REACCIONES EN LA INTERFASE. CMO AFECTA LA

AGITACIN A LA CATLISIS?

Vernica Luque-Agudo, M. Victoria Gil lvarez

IACYS-Unidad de Qumica Verde y Desarrollo Sostenible, Departamento de Qumica Orgnica

e Inorgnica, Facultad de Ciencias, Universidad de Extremadura, Avda. de Elvas, s/n, 06006

Badajoz. [email protected]

En el ao 2005, Sharpless y col. [1] definieron y aplicaron las condiciones de reactividad on

water a cicloadiciones Diels-Alder, observando un notable aumento de velocidad. La novedad

de esta tcnica de catlisis radicaba en que empleaban un medio de reaccin, el agua, que

tradicionalmente no se asociaba a productos orgnicos, dada la insolubilidad y/o poca

estabilidad de los mismos en ella. Sin embargo, los procesos no ocurran en disolucin, sino en

la interfase entre la fase orgnica y la fase acuosa. Debido a ello, esta interfase debe estar

formndose de manera continua, para que los sitios catalticos activos se renueven y estn

disponibles para las molculas de los reactivos. As, el tipo de agitacin aplicada influye

marcadamente en la eficacia de la catlisis, debiendo ser anrquica y vigorosa. Por ello, no

existe un mtodo de agitacin ideal y nico para aplicar a todas las transformaciones on

water, sino que debe ser determinado empricamente para cada reaccin [2].

Por este motivo, decidimos estudiar, por una parte, la influencia de la agitacin sobre las

reacciones on water entre furano y derivados y diversas maleimidas [3], y entre dichos

furanos y tri-O-acetil-2-nitro-D-glucal [4], un carbohidrato muy poco reactivo (Esquema 1). Los

procesos se llevaron a cabo bajo la agitacin proporcionada por un agitador magntico y un

brazo agitador de vibracin oscilante vertical. Se observ que, para el segundo conjunto de

reacciones, la velocidad y los productos formados dependan del mtodo de agitacin, siendo

posible as dirigir la transformacin hacia la obtencin de unos productos u otros.

Esquema 1

Agradecimientos

Al Gobierno de Extremadura-Ayuda a Grupos de Investigacin Catalogados y Fondo Europeo de Desarrollo Regional (Grant GR15022) y al Plan de Iniciacin a la Investigacin, Desarrollo Tecnolgico e Innovacin 2016 de la Universidad de Extremadura por la beca concedida a Vernica Luque-Agudo.

Referencias

[1] S. Narayan, J. Muldoon, M. G. Finn, V. V. Fokin, H. C. Kolb y K. B. Sharpless, Angewandte Chemie International

Edition, 2005, 44, 3275.

[2] M. C. Pirrung, K. D. Sarma y J. Wang, Journal of Organic Chemistry, 2008, 73, 8723.

[3] M. V. Gil, V. Luque-Agudo, E. Romn y J. A. Serrano, Synlett, 2014, 25, 2179.

[4] V. Luque-Agudo, M. V. Gil, E. Romn y J. A. Serrano, Green Chemistry, 2016, 18, 3844.

27


GRAPHENE, THE STAR MEMBER OF CARBON ALLOTROPES:

MECHANOCHEMICAL PREPARATION AND APPLICATIONS IN

MATERIALS SCIENCE.

Jose M. Gonzlez-Domnguez,1 C. Martn,

1 V. Len,

1 M. I. Luco,

1 S. Merino,

1,2 E. Vzquez

1,2

1Instituto Regional de Investigacin Cientfica Aplicada (IRICA), Universidad de Castilla-La

Mancha, 13071 Ciudad Real, Spain; 2Facultad de Ciencias y Tecnologas Qumicas,

Universidad de Castilla-La Mancha, Avda. Camilo Jos Cela S/N, 13071, Ciudad Real, Spain.

[email protected]

Graphene is a two-dimensional, one-atom-thick material, entirely made of carbon atoms,

arranged in a honeycomb lattice. Because of their distinctive mechanical (such as high strength

and flexibility) and electronic (great electrical and thermal conductivities) properties, graphene

and its derivatives are ideal candidates in a variety of applications [1], thus it has just started to

be engineered in electronics, photonics and polymer-based composites. However, a reliable

and scalable graphene production still stands as a bottleneck for its broad use. Fields such as

nanocomposite materials or nanomedicine require larger quantities, and have therefore used

chemical derivatives of graphene (namely its oxide, graphene oxide, GO, and its reduced

counterpart, reduced graphene oxide, rGO) instead, because these derivatives can be

produced in huge amounts practically in any laboratory. While these are very interesting

materials, their properties are markedly different from those of pristine graphene [1]. There

currently exist detailed preparation and functionalization methods for GO and rGO, but much

less is available for non-oxidized graphene.

An accessible way to obtain cost-effective and suitable large amounts of non-oxidized graphene

is the mechanochemical (e.g. by ball milling) exfoliation of graphite [2]. These methods provide

mostly few-layer graphene materials with reasonable sizes, acceptable level of defects and

good structural characteristics to enable their exploitation, for example, in composite or medical

applications. A main constraint related to the graphene development is that, being of strongly

hydrophobic nature, the majority or totality of dispersions (usually required for its handling and

processing towards the desired application) are prepared in poisonous organic solvents, such

as DMF or NMP. In light of the above mentioned, we detail a protocol (fully devised and

optimized in our laboratories [3]) that describes the preparation of exfoliated graphite down to

few-layer graphene (3-4 layers thick and ~ 500 nm diameter in average) in high yield by the use

of ball milling, its storage in the form of light solid and its easy dispersion in aqueous media. All

these set of features are rarely met simultaneously [2,3], and owing to this, we have opened

new venues for the use of graphene. Several example applications will be described, namely

the fabrication of hybrid hydrogels that take advantage of our graphenes aqueous dispersibility,

with potential applications in electromechanical sensing [4], stretch-triggered drug delivery [4]

and as biocompatible scaffolds for neuronal growth [5].

References

[1] G. Reina, J. M. Gonzlez-Domnguez, A. Criado, E. Vzquez, A. Bianco, M. Prato. Chemical Society Reviews, 2017,

46, 4400.

[2] V. Len, J. M. Gonzlez-Domnguez, J. L. G. Fierro, M. Prato, E. Vzquez. Nanoscale, 2016, 8, 14548.

[3] J. M. Gonzlez-Domnguez, V. Len, M. I. Luco, M. Prato, E. Vzquez. Nature Protocols, (in revision).

[4] J. M. Gonzlez-Domnguez, C. Martn, O. J. Dur, S. Merino, E. Vzquez. Submitted.

[5] C. Martn, S. Merino, J. M. Gonzlez-Domnguez, R. Rauti, L. Ballerini, M. Prato, E. Vzquez. Scientific Reports,

2017, 7, 10942.

28


SNTESIS QUIMIOSELECTIVA DE BENZIMIDAZOLES Y CIANOSILILACIN

DE COMPUESTOS CARBONLICOS: ACTIVIDAD CATALTICA DE Al-ITQ-HB

Sergio Rojas-Buzo, Pilar Garca-Garca, Avelino Corma

Instituto de Tecnologa Qumica (UPV-CSIC), Av. dels Tarongers, 46022, Valencia,

[email protected], [email protected]

En los ltimos aos han sido muchos los cientficos que han centrado sus estudios en la

bsqueda de nuevos catalizadores que se aproximen a la actividad presente en las enzimas

naturales. Tales materiales como las zeolitas [1], ciclodextrinas y los MOFs [2] (Metal-organic

frameworks) han sido diseados para imitar la actividad y selectividad presente en ellas y

adems con la idea de que puedan ser reusados y reutilizados. Los MOFs son materiales

basados en iones o clsteres metlicos conectados por ligandos orgnicos y formando redes

2D y 3D. Este tipo de materiales pueden ser modificados a nivel de ligando y de nodo metlico

lo que permite controlar el tamao de los canales y por lo tanto modificar la selectividad para su

aplicacin en distintos procesos qumicos de inters industrial.

Encaminados hacia esta idea, en nuestro grupo se ha diseado un nuevo material hbrido

metal-orgnico que hemos denominado Al-ITQ-HB [3], que consiste en nodos octadricos de

AlO6 unidos mediante ligandos orgnicos del tipo cido 4-heptilbenzico. La cadena

hidrocarbonada presente en este ligando favorece la formacin de fases laminares y

mesoscpicas, dando lugar a cavidades hidrofbicas que juegan un rol muy importante en la

catlisis. As pues, se ha demostrado la aceleracin en reacciones como la condensacin de

Koevenagel, la sntesis de spirooxindoles y en organometlicas asimtricas de tipo Michael [3].

Como parte de nuestro propsito de continuar descubriendo procesos sostenibles para la

obtencin de molculas de inters en qumica fina, hemos estudiado la actividad de nuestro

catalizador en la sntesis quimioselectiva de benzimidazoles y en la cianosililacin de

compuestos carbonlicos [4].

La reaccin entre aldehdos y diaminas da lugar a una mezcla compleja de productos. El ms

interesante de todos ellos es el benzimidazol ya que se utiliza de manera abundante en la

industria farmacutica. Es necesario pues el uso de un catalizador que permita obtener de

manera selectiva dicho compuesto. Con tan solo un 6 mol% de Al-ITQ-HB, se puede obtener

un 94 % del producto deseado en condiciones suaves de reaccin.

En la reaccin de cianosililacin se ha utilizado la acetofenona como sustrato modelo. La

cianohidrina correspondiente se forma tan slo con un 0,5 mol% de carga de catalizador.

Adems, el material se puede reutilizar de forma sucesiva al menos 8 veces sin prdidas

significativas en cuanto a actividad se refiere.

Referencias

[1] A. Corma, H. Garcia, European Journal of Inorganic Chemistry, 2004, 1143.

[2] Y. G. Sun, X. M. Yan, F. Ding, E. J. Gao, W. Z. Zhang, F. Verpoort, Inorganic Chemistry Communications, 2008, 11,

1117.

[3] P. Garcia-Garcia, J. M. Moreno, U. Diaz, M. Bruix, A. Corma, Nature Communications, 2016, 10835.

[4] S. Rojas-Buzo, P. Garcia-Garcia, A. Corma, ChemCatChem, 2017, 9, 997.

29
mailto:[email protected]:[email protected]

COMUNICACIONES

Orales


EvaporationWater

+ Sonication

Gelator

Organic solvent Water

400 nm

SELF-ASSEMBLED MOLECULAR NANOPARTICLES WITH POTENTIAL BIOMEDICAL APPLICATIONS

Ana Torres-Martnez, Francisco Galindo, Juan F. Miravet

Department of Inorganic and Organic Chemistry, Universitat Jaume I,

Av. de Vicent Sos Baynat, s/n, 12071, Castelln de la Plana, Spain. [email protected]

Nanomedicine has emerged in the last years as an interdisciplinary area with the use of

nanostructures for the transport and release of different molecules. The need for these

nanocarriers arises from the increasing number of therapeutic and diagnostic agents whose

efficacy is affected by nonspecific cell and tissue biodistribution, poor solubility or rapid

metabolization and excretion. Miniaturization to nanoscale provides materials with a large

surface area for bioconjugation, long circulation time in blood, and tunable size with the

possibility of being actively or passively targeted to the desired site of action [1].

Among promising nanocarriers, nanogels have attracted much attention because, as hydrogels,

they show high water content and biocompatibility. Other advantages are their simple

preparation, high loading capacity, stability and responsiveness to environmental factors (such

as ionic strength, pH and temperature). They have been reported to deliver their payload inside

cells and to increase drug delivery across biological barriers [2].

Molecular gels, formed by the non-covalent association of low molecular weight molecules,

have been extensively studied and present lots of potential applications (controlled release,

tissue engineering, catalysis or optoelectronics) [3]. Although only polymeric nanogels have

been studied so far, molecular gels characteristics make them appealing: they present a fully

reversible and stimuli-regulated assembly and an easier biodegradation due to their small-

molecule structure.

We present here the preparation and characterization of a new type of nanoparticles (ca. 100

nm) formed by self-assembled molecular gels. The approach used is the ultrasound-promoted

nanogel formation, a fast and reproducible process [4]. The loading, stability and controlled

release of different photoactive molecules has been studied, including in vitro experiments.

References

[1] G. Chen, I. Roy, C. Yang and P. N. Prasad, Chemical Reviews, 2016, 116, 2826.

[2] A. V. Kabanov and S. V. Vinogradov, Angewandte Chemie, 2009, 48, 5418.

[3] R. G. Weiss, Journal of the American Chemical Society, 2014, 136, 7519.

[4] X. Yan, Y. Cui, W. Qi, Y. Su, Y. Yang, Q. He and J. Li, Small, 2008, 4, 1687.

31


SYNTHESIS OF Au(I)- AND Au(III)-Bis(NHC) COMPLEXES:

LIGAND EFFECT ON OXIDATIVE ADDITION

Alba Collado,1,2,3

Jan Bohnenberger, Steven P. Nolan

1Current address:

Departamento de Qumica Orgnica I, Facultad de Qumica, Universidad

Complutense, 28040-Madrid, Spain;2 Current address:

Centro de Innovacin en Qumica

Avanzada (ORFEO-CINQA); 3

Address where the work was carried out: EaStCHEM, School of

Chemistry University of St. Andrews, Purdie Building, North Haugh, St. Andrews, Fife, KY16

9ST (UK). [email protected]

The field of homogenous gold catalysis has exponentially grown in the last decade [1]. In this

area of research, most catalytic reports employ Au complexes in oxidation state +1. In contrast,

the catalytic activity of gold(III) species has been much less developed [2]. The main reason for

this is mainly the intrinsic tendency of Au(III) complexes to reduce to Au(I) or Au(0) in the

reaction media. In addition, the Au(III) species that have proven to be stable to be isolated are

usually too stable to be used in catalytic reactions [2]. Recently, the field of gold redox catalysis,

where both Au(I) and Au(III) species are involved, has allowed for the development of

fascinating chemistry [3]. In this context, much interest has arisen around the synthesis of new

Au(III) species with catalytic potential, and the study of the elementary steps of the gold redox

catalytic cycle.

Due to the relevance of N-Heterocyclic carbene (NHC) ligands in gold catalysis, a family of

Au(I)-bis(NHC) complexes has been synthesised and their oxidation chemistry towards

hypervalent iodine oxidants, which are common oxidants in gold redox catalysis, has been

explored. This study revealed a ligand influence on the formation of Au(III) species and has

allowed for the design of new Au(III) complexes [4].

References

[1] A. S. K. Hashmi, Chemical Reviews, 2007, 107, 3180.

[2] a), C.-Y. Wu, T. Horibe, C. B. Jacobsen, F. D. Toste, Nature, 2015, 517, 449; b) H. Schmidbaur, A. Schier,

Arabian Journal for Science and Engineering, 2012, 37, 1187.

[3] a) L. T. Ball, G. C. Lloyd-Jones, C. A. Russell, Science, 2012, 337, 1644; b) T. D. Haro, C. Nevado, C., Journal of

American Chemical Society, 2010, 132, 1512.

[4] A. Collado, J. Bohnenberger, M. J. Oliva-Madrid, P. Nun, D. B. Cordes, A. M. Z. Slawin, and S. P. Nolan, S. P.

European Journal of Inorganic Chemistry, 2016, 25, 4111.

32


LARGEST SOLUBLE AND ATOMICALLY-PRECISE GRAPHENE-LIKE

NANORIBBONS BASED ON AZAACENES

Diego Cortizo-Lacalle1, Aurelio Mateo-Alonso

2

POLYMAT, University of the Basque Country UPV/EHU Avenida de Tolosa 72, E-20018

Donostia-San Sebastian, Spain. [email protected]

Linear and ribbon-like polycyclic aromatic hydrocarbons such as acenes and graphene nanoribbons have recently attracted large interest from the scientists, as they can be considered as graphene cut outs designed ad libitum. By careful and wise control of their synthesis, the major drawbacks of the graphene, such as zero band-gap or neglible solubility, can be overcome while retaining the one-atom thickness of graphene with the structure-dependent metallicity of carbon nanotubes.

In general, the nanoribbons can be obtained by following either a top-down or bottom-up approach. Although, the former has been widely used by cutting graphene or unzipping carbon nanotubes to prepare NRs, the NRs do not show atomic precision over any structural variable. Bottom-up can provide atomically-precise control over the edges of the NRs, but do not provide control over the length. Solution polymerisation methods provide control over the edge and width, but no control over the length.

The properties of NRs are highly dependent on the width, length and edge structure, and therefore, a precise atomic control over these three structural variables is necessary for establishing their fundamental properties and exploring their potential applications. NRs have unique electronic, optical and mechanical properties and are considered promising candidates to develop new technologies for electronics, photonics, and energy conversion, among others.

Here, we present a series of the largest atomically precise NRs which are based on pyrene-fused pyrazaacenes [1]. Due to the introduction of pyrene units into the backbone, this type of nitrogenated polycyclic aromatic hydrocarbons show very high stability in air. The nanoribbons were easily characterised due to the large solubility in common organic solvents and the photoconductivity measured.

References

[1] A. Mateo-Alonso, Chemical Society Reviews, 2014, 43, 6311.

33


DESARROLLO DE EMULSIONES ECOLGICAS POR

MICROFLUIDIZACIN. EFECTO DE LA PRESIN Y EL TIPO DE CMARA

DE INTERACCIN

Luis A. Trujillo-Cayado, Jenifer Santos, Pablo Ramrez, M Carmen Alfaro, Jos Muoz

Departamento de Ingeniera Qumica, Facultad de Qumica, Universidad de Sevilla, C/ Profesor Garca Gonzlez S/N, 41004, Sevilla. [email protected]

El objetivo de esta investigacin ha sido desarrollar emulsiones aceite-en-agua ecolgicas mediante microfluidizacin, estudiando principalmente la influencia de la presin de homogenizacin y el tipo de cmara utilizada. El disolvente utilizado como fase dispersa ha

sido -pineno, un terpeno primario que se encuentra en la naturaleza como componente de aceites esenciales como el de romero y puede obtenerse adems a partir de varias especies de rboles y arbustos, en especial del pino [1]. Se estudiaron previamente las propiedades

superficiales (aire/agua) e interfaciales (-pineno/agua) del agente emulsionante utilizado, un tensioactivo no inico comercial derivado del aceite de coco (Levenol F-200) y que est considerado como compuesto ecolgico, mediante tensiometra de gota pendiente. Las emulsiones se han preparado con una concentracin de fase oleosa del 30% p/p y de agente emulsionante del 3% p/p mediante microfludica, haciendo uso de presiones comprendidas en el intervalo 5000-25000 psi y dos configuraciones distintas de cmaras de interaccin (Y o Y+Z). Las tcnicas utilizadas para caracterizar las emulsiones han sido: la reologa, la difrac-cin lser, multiple light scattering, microscopa ptica y Cryo-SEM. Los resultados de la caracterizacin interfacial han puesto de manifiesto las buenas propiedades superficiales de

este tensioactivo en ambas interfases. En el caso de la interfase -pineno/agua, el tensioactivo reduce considerable y rpidamente la tensin interfacial. Se ha demostrado que el uso del tensioactivo Levenol F-200 produce emulsiones con tamao submicrnico independientemente de la presin y configuracin de cmara de interaccin utilizada. La mayor estabilidad fsica se obtuvo para las emulsiones procesadas con la configuracin Y+Z a 25000 psi debido a sus menores tamaos de gota, lo que ayuda a prevenir fenmenos de desestabilizacin como el cremado o la coalescencia. En general, el uso de las dos cmaras y un incremento de la presin ha conllevado la reduccin de los dimetros medios de gota y de la polidispersidad. La monitorizacin de la estabilidad fsica por multiple light scattering ha demostrado que el mecanismo de desestabilizacin dominante de todas las emulsiones es el cremado, aunque no se haya producido separacin de fases observable a la vista. Esto se ha atribuido a que, a pesar de que el tamao de gota es muy pequeo, la movilidad de las gotas estaba favorecida por la baja viscosidad de las emulsiones. Por ello, la emulsin con menor valor del Turbiscan Stability Index [2] fue formulada nuevamente utilizando como estabilizante fsico una arcilla comercial (Aerosil 200), aumentando la viscosidad y disminuyendo la desestabilizacin por cremado. De esta forma, se han conseguido emulsiones de alta estabilidad fsica, tamao de gota submicrnico y con propiedades reolgicas mejoradas y modulables.

Agradecimientos

Este trabajo forma parte de los resultados obtenidos en el proyecto CTQ2015-70700-P, financiado por el Ministerio de Economa y Competitividad del Gobierno de Espaa y por la Comisin Europea (Programa FEDER).

Referencias

[1] K.H.C. Baser, G. Buchbauer (Eds.), Handbook of essential oils: science, technology, and applications, CRC Press,2009.

[2] L.A. Trujilo-Cayado, M.C. Garca, J. Santos, J.A. Carmona, M.C. Alfaro, ACS Sustainable Chemistry & Engineering,2017, 5, 4127.

34


OXIDATIVE ACTIVATION OF C-S BONDS WITH AN ELECTROPOSITIVE

NITROGEN PROMOTER ENABLES ORTHOGONAL GLYCOSYLATION OF

ALKYL OVER PHENYL THIOGLYCOSIDES

Ester Jimnez-Moreno,1 Annabel Kitowski,

1,2 Mriam Salvad,

1,3 Jordi Mestre,

3 Sergio Castilln,

3

Gonzalo Jimnez-Oss,4 Omar Boutureira,

3 Gonalo J. L. Bernardes

1,2

1Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW Cambridge (UK);

2Instituto de Medicina Molecular, Faculdade de Medicina, Universidade de Lisboa,

Avenida Professor Egas Moniz, 1649028 Lisboa (Portugal); 3Departament de Qumica

Analtica i Qumica Orgnica, Universitat Rovira i Virgili, C/ Marcell Domingo 1, 43007 Tarragona (Spain);

4Departamento de Qumica, Centro de Investigacin en Sntesis Qumica,

Universidad de La Rioja, 26006 Logroo (Spain). [email protected]

Carbohydrates represent one of the largest groups of key biomolecules since they are involved in many essential biological processes [1]. For a better understanding of their roles in biological systems, as well as for the development of carbohydrate-based therapeutics and vaccines [2], it is key to access chemically defined oligosaccharides. Thus, efforts have been devoted to the development of efficient methods that allow their controlled synthesis [3].

Here, we present a method for the selective activation of thioglycosides that uses the N+-

thiophilic reagent O-mesitylenesulfonylhydroxylamine (MSH) as a promoter. The reaction proceeds via anomeric mesitylensulfonate intermediates, which could be isolated and fully characterized by placing a fluorine atom at the C-2 position. In the presence of a soft Lewis acid, glycosylation reaction proceeds at ambient temperature with good yields. We further demonstrate that it is possible to orthogonally activate S-ethyl in the presence of S-phenyl donors enabling the design of sequential glycosylation strategies.

Acknowledgments

We thank the European Commission (Marie Curie CIG and Marie Skodowska-Curie ITN project ProteinConjugates to G.J.L.B. and A.K; Marie Skodowska-Curie IEF to E.J.M.), MINECO (RYC-2015-17705 to O.B. and CTQ2015-70524-R and RYC-2013-14706 to G.J.O.), FCT Portugal (FCT Investigator to G.J.L.B.), the European Regional Development Fund, Generalitat de Catalunya (M.S), and the Universitat Rovira i Virgili (Mart Franqus Research Fellowship Programme to J.M.) for financial support. BIFI (Memento cluster) is acknowledged for computer support. G.J.L.B. is a Royal Society University Research Fellow and holds an ERC Starting Grant (TagIt).

References

[1] K. Ohtsubo, J. D. Marth, Cell, 2006, 126, 855.[2] R. Adamo, A. Nilo, B. Castagner, O. Boutureira, F. Berti, G. J. L. Bernardes, Chemical Science, 2013, 4, 2995.[3] G. J. L. Bernardes, B. Castagner, P. H. Seeberger, ACS Chemical Biology, 2009, 4, 703713.

35


FLUORESCENCIA FRONT-FACE COMBINADA CON QUIMIOMETRA PARA

EL ESTUDIO DEL PERFIL FENLICO DE UVAS CON DIFERENTES

REGMENES HDRICOS

Manuel Cabrera-Baegil1, Esperanza Valds-Snchez

2, Daniel Moreno

2, Isabel Durn-Mers

1

1Departamento Qumica Analtica e IACYS, Facultad de Ciencias, Universidad de Extremadura,

Avda. de Elvas, 06006, Badajoz; 2Departamento de Enologa, Instituto Tecnolgico

Agroalimentario de Extremadura, Centro de Investigaciones Cientficas y Tecnolgicas de

Extremadura (CICYTEX), Avda. Adolfo Surez S/N, 06007, Badajoz. [email protected]

Las prcticas agronmicas son una excelente herramienta para dar respuestas a las demandas de calidad de los consumidores. Entre ellas, la aplicacin de riego en el viedo afecta a la composicin fenlica de las uvas y su estudio es necesario para mejorar la acumulacin de fenoles y obtener un adecuado compromiso entre rendimiento y calidad. La acumulacin de estas sustancias en las uvas supone un valor aadido en el producto ya que las mismas previenen el desarrollo de ciertas enfermedades [1]. Sin embargo, el anlisis individual de los compuestos fenlicos requiere tcnicas caras como la cromatografa de lquidos en la que se emplean largos tiempos de elucin y requiere un personal con formacin en esas tcnicas. Por lo tanto, el desarrollo de mtodos de determinacin de compuestos fenlicos rpidos, simples, baratos y con mnimo tratamiento de muestras es necesario para que el sector enolgico pueda disponer de ellos. A partir de la fluorescencia nativa de los alimentos en combinacin con algoritmos quimiomtricos se puede obtener informacin que permita la caracterizacin de los mismos. Aplicando esta metodologa, en el caso de los vinos, se ha llevado a cabo el anlisis de compuestos fenlicos [2].

En este trabajo se van a estudiar mediante fluorescencia front-face, extractos de uva sometidos a diferentes regmenes hdricos y la informacin obtenida se analizar con herramientas quimiomtricas como Parallel Factor Analisys (PARAFAC) y U-PLS con el objetivo de diferenciar entre los distintos regmenes hdricos. Para ello se registraron matrices de excitacin-emisin, y la representacin de los valores de los scores de PARAFAC de manera tridimensional, nos permiti diferenciar entre los diferentes tipos de uvas. Por otra parte, se realiz una calibracin en ter para la cuantificacin de catequina, epicatequina y resveratrol. Se correlacionaron los scores del primer componente de PARAFAC con las concentraciones de resveratrol (r

2=0.897) y los del tercero con la suma de concentraciones de catequina y

epicatequina (r2=0.940). Finalmente, se analizaron las muestras de uva por fluorescencia y por

cromatografa de lquidos, encontrndose buena concordancia entre los resultados obtenidos por ambos mtodos. La concentracin de resveratrol por U-PLS fue 2.640.71 mg/kg para muestras de secano y 4.400.21 mg/kg para muestras de regado. En el caso de la suma de catequina y epicatequina, las mejores predicciones se obtuvieron por PARAFAC y fueron 20.621.23 mg/kg para uvas de secano y 32.550.78 mg/kg.

Agradecimientos

Manuel Cabrera-Baegil e Isabel Durn-Mers agradecen al Ministerio de Economa y Competitividad (CTQ2014-52309-P) y a la Junta de Extremadura (GR15090-Ayuda a grupo de investigacin FQM003 y proyecto IB16055), ambos cofinanciados por el fondo europeo de desarrollo regional. Manuel Cabrera-Baegil agradece el patrocinio de la Comunidad Autnoma de Extremadura, a la Consejera de Economa e Infraestructuras y la cofinanciacin del Fondo Social Europeo (FSE) por el contrato predoctoral (PD16015).

Referencias

[1] P. Saiki, A. Szakmary, W. Jaeger, T. Szekeres, Mutation Research/Reviews in Mutation Research, 2008, 658, 68.

[2] M. Cabrera-Baegil, M.C. Hurtado-Snchez, T. Galeano-Daz, I. Durn-Mers, Food Chemistry, 2017, 220, 168.

36


FORMATION OF C-C, C-S AND C-N BONDS CATALYSED BY SUPPORTED

COPPER NANOPARTICLES

Iris Martn-Garca,1 Alexander Yu. Mitrofanov,

2 Arina V. Murashkina,

2 Francisco Alonso,

1 Irina P.

Beletskaya2

1Instituto de Sntesis Orgnica (ISO) and Departamento de Qumica Orgnica, Facultad de

Ciencias, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain; 2Department of Chemistry,

Moscow State University, Leninskie Gory, GSP-1, Moscow 119991, Russia. [email protected]

Transition-metal catalysed cross-coupling reactions are still dominated by palladium chemistry.

For instance, we have, recently, reported an efficient catalytic system based on PdNPs/DNA

applicable to the copper- and ligand-free Sonogashira-Hagihara reaction [1]. The catalyst is

used with low Pd loading under mild conditions in MeOH without air exclusion. In addition, it can

be reused in five cycles and shows better performance than an array of commercial Pd

catalysts.

Within the recent past, copper has gained ground against palladium by virtue of its cheaper

price and equivalent function in certain reactions [2]. Four catalysts consisting of copper

nanoparticles on zeolite [3a], titania [3b], montmorillonite and activated carbon [3c] have been

tested in three palladium- and ligand-free cross-coupling reactions to form carboncarbon [4],

carbonsulfur [5] and carbonnitrogen [6] bonds [7].

Among these catalysts, CuNPs/zeolite has been found to be the best one in the Sonogashira

reaction of aryl iodides and aryl acetylenes, as well as in the coupling of aryl halides with aryl

and alkyl thiols, being reusable in both cases. In the case of the arylation of nitrogen-containing

heterocycles (imidazole, pyrazole, benzimidazole and indole), it has been better accomplished

with CuNPs/titania, albeit CuNPs/activated carbon showed better recycling properties.

The catalytic activity of the nanostructured catalysts has been compared with that of twelve

commercial copper catalysts, with the former outperforming the latter in the three types of

reactions studied. Therefore, taking into account that our catalysts are easily prepared, the

protocols introduced in this report are an attractive alternative to the utilisation of the more

expensive palladium catalysts and the commercial (non-reusable) copper catalysts.

References

[1] A. S. Camacho, I. Martn-Garca, C. Contreras-Celedn, L. Chacn-Garca and F. Alonso, Catalysis Science and

Technology, 2017, 7, 2262.

[2] C. Maaliki, E. Thiery and J. Thibonnet, European Journal of Organic Chemistry, 2017, 209.

[3] a) F. Alonso, A. Arroyo, I. Martn-Garca, Y. Moglie, Advanced Synthesis and Catalysis, 2015, 357, 3549; b) F.

Alonso, T. Melkonian, Y. Moglie, M. Yus, European Journal of Organic Chemistry, 2011, 13, 2524; c) F. Alonso, Y.

Moglie, G. Radivoy, Accounts of Chemical Research, 2015, 48, 2516.

[4] Reviews: a) M. Karak, L. C. A. Barbosa and G. C. Hargaden, RSC Advances, 4 (2014), 53442-53466. b) A. M.

Thomas, A.l Sujatha and G. Anilkumar, RSC Advances, 2014, 4, 21688.

[5] A. Sujatha, A. M. Thomas, A. P. Amrutha and G. Anilkumar, Arkivoc, 2015, 1.

[6] a) J. Bariwalab, E. Van der Eycken, Chemical Society Reviews, 2013, 42, 9283; b) K. Okano, H. Tohuyama and T.

Fukuyama, Chemical Communications, 2014, 50, 13650.

[7] A. Y. Mitrofanov, S. V. Murashkina, I. Martn-Garca, F. Alonso, I. P. Beletskaya, Catalysis Science and Technology,

2017, DOI: 10.1039/c7cy01343d.

37


REDES METAL-ORGNICAS COMO VEHCULOS PARA LA LIBERACIN

TERAPUTICA DE MONXIDO DE CARBONO

C. R. Maldonado1, F. J. Carmona

1, S. Rojas

1, C. Romo

2, S. Furukawa

3, S. Kitagawa

3, J. A. R.

Navarro1, E. Barea

1

1Departamento de Qumica Inorgnica, Universidad de Granada, Av. Fuentenueva S/N, 18071

Granada, Espaa; 2Alfama Inc. e Instituto de Tecnologia Qumica e Biolgica da Universidade

Nova de Lisboa, Av. da Repblica, EAN, 2780-157 Oeiras, Portugal; 3 Institute for Integrated

Cell-Material Sciences (iCeMS), Kyoto University, Yoshidahonmachi, Sakyo-ku, 606-8501

Kyoto, Japn. [email protected]

Recientemente se ha demostrado que el monxido de carbono (CO) es una importante

molcula bioseal que puede ejercer un efecto teraputico beneficioso/homeosttico en el

organismo y, en concreto, en el tratamiento de dolencias de tipo inflamatorio y/o cardiovascular,

as como en la preservacin de rganos para trasplantes [1]. Aunque la simple inhalacin de

mezclas aire/CO sera la va de administracin ms sencilla para este gas, desgraciadamente

esta ruta de administracin carece de especificidad y, por lo tanto, requerira que el paciente

inhalase grandes dosis del mismo.

En este contexto, los materiales liberadores de CO (CORMAs) [2] surgen como una va de

administracin ms segura y especfica. Los CORMAs se definen como sistemas slidos

avanzados capaces de almacenar CO y suministrarlo posteriormente, de forma controlada en

el tiempo, mediante la aplicacin de un estmulo apropiado (cambio de pH, luz, presencia de

una determinada enzima, etc). Una de las estrategias ms verstiles para disear nuevos

CORMAs consiste en la combinacin de un carbonilo metlico, que acta como prodroga de

CO, y una plataforma/vehculo biocompatible. En este sentido, las redes metal-orgnicas

(MOFs) ofrecen la posibilidad de albergar en sus poros grandes cantidades del profrmaco de

CO, evitando su prematura degradacin en el medio fisiolgico, as como de retener en sus

cavidades los fragmentos de decarbonilacin metlicos potencialmente txicos.

Teniendo en cuenta estos antecedentes, en esta

comunicacin, se presentan mltiples

estrategias (ej. intercambio inico [3], uso de

MOFs de estructura jerarquizada [4], empleo del

mtodo de modulacin de la coordinacin) para

la preparacin de nuevos CORMAs basados en

diferentes polmeros de coordinacin porosos y

el CORM fotoactivo ALF794

([Mo(CNCMe2CO2H)3(CO)3]). En todos los casos, tanto la cintica de liberacin de CO como el porcentaje de lixiviacin de los fragmentos

metlicos en medio fisiolgico de los materiales hbridos resultantes han sido evaluados.

Agradecimientos

Al Ministerio de Economa y Competitividad (CTQ2014-53486R y contrato postdoctoral Juan de la Cierva de CRM), a

la accin COST CM1105 y a la UGR (contrato de reincorporacin para jvenes investigadores doctores de CRM).

Referencias

[1] R. Motterlini, L.E. Otterbein, Nature Reviews Drug Discovery, 2010, 9, 728.

[2] S.H. Heinemann, T. Hoshi, M. Westerhausen, A. Schiller, Chemical Communications, 2014, 50, 3644.

[3] F.J. Carmona, S. Rojas, P. Snchez, H. Jeremias, A.R. Marques, C.C. Romo, D. Choquesillo-Lazarte, J.A.R.Navarro, C.R. Maldonado, E. Barea, Inorganic Chemistry, 2016, 55, 6525. (selected as ACS Editors Choice)

[4] F.J. Carmona, S. Rojas, C.C. Romo, J.A.R. Navarro, E. Barea, C.R. Maldonado, Chemical Communications, 2017,53, 6581.

38


ENANTIO-, AND DIASTEREOSELECTIVE CYCLOPROPANATION OF 1-

ALKENYLBORONATES: SYNTHESIS OF 2,3-SUBSTITUTED

BOROCYCLOPROPANES

J. Carreras, A. Caballero, P. J. Prez

Laboratorio de Catlisis Homognea, Unidad Asociada al CSIC, CIQSO-Centro de

Investigacin en Qumica Sostenible, Departamento de Qumica, Universidad de Huelva.

[email protected]

Substituted cyclopropane rings are present in numerous natural and synthetic products with important biological activities [1]. More than 4000 natural products have been isolated with this structural motif. Densely functionalized cyclopropanes also find applications in drug discovery [2] and since the 60s have been routinely included in SAR studies of new drug candidates, inorder to modulate their activity, metabolism or conformational rigidity. Therefore, astraightforward access to building blocks containing enantiopure cyclopropanes is of greatinterest.

Despite the progress in the synthesis of cyclopropane derivatives, there are only a few strategies of the preparation of optically active cyclopropylboronates reported in the literature [3]. We decided to explore the synthesis of 2,3-substituted borocyclopropanes as a versatile cyclopropane subunit, by a two-step approach of hydroboration and enantioselective cyclopropanation, using alkynes as starting materials (Scheme 1). We also investigated the development of this strategy in a sequential fashion, to avoid the purification of the alkenylboronate. The results on this method for the preparation of this type of highly substituted borocyclopropanes, as well as further functionalization in the cyclopropane ring will be presented.

Scheme 1

Acknowledgements

This work was supported by the MINECO (CTQ2014-52769-C3-1-R). J.C. thanks MINECO for Juan de la Cierva-

Incorporacin fellow (IJCI-2014-19161).

References

[1] a) J. Pietruszka Chemical Reviews, 2003, 103, 1051; b) D. Y.-K. Chen, R. H. Pouwer, J.-A. Richard ChemicalSociety Reviews, 2012, 41, 4631.

[2] T. T. Talele, Journal of Medicinal Chemistry, 2016, 59, 8712.

[3] a) L. E. Zimmer, A. B. Charette Journal of the American Chemistry Society, 2009, 131, 15624; b) C. Zhong, S. Kunii,Y. Kosaka, M. Sawamura, H. Ito, Journal of the American Chemistry Society, 2010, 132, 11440; c) A. Parra, L. AmensM. Guisn-Ceinos, A. Lpez, J. L. Garca Ruano, M. Tortosa, Journal of the American Chemistry Society, 2014, 136,15833 and references cited therein.

39


NEW INHIBITORS OF PARASITIC CYSTEINE PROTEASES

L. Bou-Iserte, A. Latorre, S. Rodrguez, F. V. Gonzlez

Department de Qumica Inorgnica i Orgnica, Escola Superior de Tecnologia I Cincies

Experimentals, Universitat Jaume I, Avenida de Vicent Sos Baynat, s/n, 12071, Castelln de la

Plana. [email protected]

Cysteine proteases belonging to papain superfamily have been recognized as interesting therapeutic targets for the search of new drugs against infectious tropical diseases such as malaria, Chagas disease, leishmaniasis and Sleeping sickness [1]. We have developed new inhibitors against cysteine proteases as Dipeptidyl epoxyesters, Dipeptidyl enoates and Aminoacyl epoxysulfones. Recently we have reported Dipeptidyl nitroalkenes as a new type of highly potent covalent reversible inhibitors of cysteine proteases (Scheme 1) [2]. These compo

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