curso académico 2015‐2016 - USC-UDC-UVI

Transcripción

9, 10 de Junio de 2016 1er MINISIMPOSIO INTERUNIVERSITARIO DEL MÁSTER EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL. Curso académico 2015‐2016
MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL
Curso académico 2015‐2016
Minisimposio Interuniversitario La asignatura Seminario de Máster incluye, entre otras actividades formativas, un Minisimposio Interuniversitario, que, en la edición del actual curso académico 2015‐2016, tendrá lugar en la Universidade da Coruña, en su Centro de Investigacións Científicas Avanzadas (CICA), los días 9 y 10 de junio. Al tratarse de una asignatura obligatoria para los alumnos de la orientación investigadora, todos ellos deben asistir y participar en este evento, asistiendo a las conferencias que se organizan y presentando cada estudiante una comunicación oral corta (5 minutos) sobre el trabajo desarrollado en la asignatura Prácticas Académicas y/o el Trabajo Fin de Máster, en gallego, castellano o inglés. Previamente, cada alumno elaborará un resumen de su comunicación, en inglés, utilizando la plantilla que se pondrá a su disposición. Este resumen debe ser enviado a la dirección de correo electrónico [email protected] con copia a [email protected] antes del próximo día 5 de mayo. La asistencia y participación en el Minisimposio será evaluada por una comisión científica integrada por profesores de las tres universidades, valiéndose de una rúbrica que se publicará previamente. La calificación obtenida será uno de los elementos a utilizar en la calificación de la asignatura Seminario de Máster. 2
MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL Curso académico 2015‐2016 Minisimposio Interuniversitario RÚBRICA PARA LA EVALUACIÓN DE COMUNICACIONES: CRITERIO DE EVALUACIÓN Resumen
ALTO (10‐9)
El resumen se ajusta completamente a las normas establecidas. NIVEL DE CUMPLIMIENTO
MEDIO (7‐8,9)
No se ajusta totalmente a las normas dadas. Expresión escrita El resumen está escrito de forma clara, fluida y correcta, por lo que se entiende fácilmente. Poco clara y fluida, lo que dificulta su comprensión. Presentación y defensa
Ajuste a las directrices establecidas ALTO
La exposición se ajusta al tiempo y normas establecidas. MEDIO
No se ajusta totalmente a las normas dadas. Presentación La presentación está bien diseñada, ordenada y estructurada. Está escrita de forma clara, fluida y correcta, por lo que se entiende fácilmente. Se emplean diversos recursos de manera adecuada durante la exposición (gráficos, tablas,…), que facilitan la comprensión. La presentación está poco ordenada y estructurada y tiene fallos de diseño. Está escrita de forma poco clara y fluida, lo que dificulta su compresión. Se utilizan recursos aunque no aportan ni aclaran. Exposición La exposición oral es clara, fluida y correcta, por lo que se entiende fácilmente. El estudiante emplea con rigor el lenguaje científico. Establece contacto visual con la audiencia y adopta una postura corporal adecuada. Contenido Los objetivos que se proponen se concretan y expresan adecuadamente. Los resultados se presentan de forma concreta y se discuten adecuadamente. Se obtienen conclusiones de forma clara, convincente y estructurada. Defensa El estudiante responde correctamente a las Responde correctamente a algunas de las preguntas realizadas. El estudiante incluso aporta preguntas realizadas. Pone ejemplos poco datos adicionales y pone ejemplos elaborados elaborados para aclarar sus respuestas. para aclarar sus respuestas. Ajuste a las normas establecidas Poca clara y fluida, lo que dificulta su comprensión. No se emplea con suficiente rigor el lenguaje científico. Establece contacto visual con la audiencia ocasionalmente. No adopta una postura corporal adecuada y que facilite la comunicación. Los objetivos que se proponen se concretan pero no se expresan adecuadamente. Se concretan los resultados pero no se discuten correctamente. Se obtienen conclusiones pero no de manera adecuada. 3
BAJO (4‐6,9) No aplica las directrices establecidas No se expresa con claridad por lo que no se entiende el mensaje. Se detectan faltas ortográficas y/o gramaticales. BAJO
No aplica las directrices establecidas. La presentación está desordenada y mal estructurada y diseñada. La expresión escrita no es clara, por lo que no se entiende el mensaje. Se detectan faltas ortográficas y/o gramaticales. No se emplea ningún recurso que facilite su comprensión. No se expresa con claridad por lo que no se entiende el mensaje. No se emplea lenguaje científico o se emplea lenguaje coloquial. No mira a la audiencia y muestra falta de control de la situación. No se plantean objetivos concretos. No existe concreción en los resultados obtenidos. No se obtienen conclusiones. No responde a las preguntas realizadas y/o lo hace de manera errónea. MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL
1er Minisimposio Interuniversitario del Máster en Investigación Química y Química Industrial (curso académico 2015‐2016) Lugar de celebración: Centro de Investigacións Científicas Avanzadas (CICA) UNIVERSIDADE DA CORUÑA As Carballeiras, s/n. Campus de Elviña 15071 A Coruña, España Fechas: 9 y 10 de junio de 2016 4 MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL
Distribución temporal de las conferencias IL = Conferencia invitada CF = comunicación tipo flash Hora Conferencia (IL, CF) 10:00‐10:45 IL5 Apertura 10:45‐10:50 CF18 11:15‐12:00 IL1 10:50‐10:55 CF19 12:00‐12:05 CF1 10:55‐11:00 CF20 12:05‐12:10 CF2 11:00‐11:05 CF21 12:10‐12:15 CF3 11:05‐11:10 CF22 12:15‐13:00 IL2 11:10‐11:15 CF23 13:00‐13:05 CF4 11:30‐12:00 Café 13:05‐13:10 CF5 12:00‐12:45 IL6 13:10‐13:15 CF6 12:45‐12:50 CF24 13:15‐13:20 CF7 12:50‐12:55 CF25 13:20‐13:25 CF8 12:55‐13:00 CF26 13:30‐15:30 Comida 13:00‐13:05 CF27 15:30‐16:15 IL3 13:05‐13:10 CF28 16:15‐16:20 CF9 13:10‐13:15 CF29 16:20‐16:25 CF10 13:15‐13:20 CF30 16:25‐16:30 CF11 13:20‐13:25 CF31 16:30‐16:35 CF12 13:30‐15:30 Comida 16:35‐16:40 CF13 15:30‐16:15 IL7 16:45‐17:15 Café 16:15‐16:20 CF32 17:15‐18:00 IL4 16:20‐16:25 CF33 18:00‐18:05 CF14 16:25‐16:30 CF34 18:05‐18:10 CF15 16:30‐17:15 IL8 18:10‐18:15 CF16 17:15‐17:30 Clausura 18:15‐18:20 CF17 Jueves 9 de junio Hora Conferencia (IL, CF) 10:30‐11:00 Café 11:00‐11:15 Viernes 10 de junio 5 MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL
PROGRAMA Jueves, 9 de junio de 2016 BIENVENIDA 10:30‐11.00 Café de bienvenida 11:00‐11.15 APERTURA DEL MINISIMPOSIO Dr. Julio Abalde Alonso Catedrático de Microbiología y Rector de la Universidade da Coruña Dr. Ramón Estévez Cabanas Catedrático de Química Orgánica de la Universidade de Santiago de Compostela y Coordinador del Máster Dr. Carlos Jiménez González Catedrático de Química Orgánica de la Universidade da Coruña y Coordinador del Minisimposio MAÑANA 11:15‐12:00 IL1 “BIOSÍNTESIS COMBINATORIA Y GENERACIÓN DE NUEVOS COMPUESTOS BIOACTIVOS EN ACTINOMICETOS” 12:00‐12:05 CF1 “Synthesis and reactivity of an aryne precursor derived from biphenylene” 12:05‐12:10 CF2 “Stereochemistry determination of macrocycles from marine sponges and synthesis of analogs of the siderophore anguibactin” 12:10‐12:15 CF3 “Palladium NPs for Arsenic and Antimony speciation followed analysis by TXRF and sample preparation strategies using microextraction techniques” 12:15‐12:30 IL2 “AGENTES DE CONTRASTE PARA IMAGEN POR RESONANCIA MAGNÉTICA BASADOS EN COMPLEJOS METÁLICOS” 13:00‐13:05 CF4 “Micro‐extraction techniques applied to biological samples of toxicological interest” 13:05‐13:10 CF5 “Development of a Ultra‐High Performance Chromatography (UHPLC) coupled to tandem MS method for simultaneous determination of pharmaceuticals and drugs in water samples” 6 Dr. José Antonio Salas Fernández
Catedrático de Microbiología Universidad de Oviedo
Berta Álvarez Pérez
USC
María Alejandra Pérez Quintiana UDC
Laura Vilas Trigo
UVIGO
Dr. Carlos Platas Iglesias
Prof. Titular de Química Inorgánica Universidade da Coruña
Ana María Ares Fuentes USC Verónica Castro Bustelo
USC
13:10‐13:15 CF6 “Preparation and characterization of functionalized palladium complexes” 13:15‐13:20 CF7 13:20‐13:25 CF8 “Preparation of magnetic nanoparticles‐
siderophores conjugates, and its possible application in pathogen detection” “Expression of recombinant proteins in C6/36 mosquito cells (Aedes Albopictus)” 13:30‐15:30 Comida TARDE 15:30‐16:15 IL3 “INTERFACIAL CHARGE TRANSFER KINETICS IN MOLECULAR SOLAR CELLS” 16:15‐16:20 CF9 “Obtaining epimers of second generation vitamin D analogs” Francisco Reigosa Chamorro
USC
Javier Cisneros Sureda
UDC
Sheila Barrios Esteban
USC
Dr. Emilio Palomares
Investigador del Institute of Chemical Research of Catalonia (ICIQ) en Tarragona
Hugo Santaballa García
UVIGO
16:20‐16:25 CF10 “Ferrimagnetic CoFe2O4 and antiferromagnetic Cr2O3 nanostructured composites” Martín Testa Anta
UVIGO
16:25‐16:30 CF11 “A Novel ZnDy Single Molecular Magnet” Julio Corredoira Vázquez
USC
16:30‐16:35 CF12 “Magnetic nanoparticles: dispersive solid phase extraction for selenium determination by electrothermal atomic adsorption spectrometry” 16:35‐16:40 CF13 “Self‐assembly of exo‐functionalized mononuclear Pd(II) and Pt(II) metallacycles” 16:45‐17:15 17:15‐18:00 IL4 Alicia Prieto Troitiño
UVIGO
Iago Neira García
UDC
Café “MATERIALES PLASMÓNICOS NANOESTRUCTURADOS: SÍNTESIS Y APLICACIONES” 18:00‐18:05 CF14 “Chiral Frameworks for the Construction of Functional Surfaces” 18:05‐18:10 CF15 “Development of Fast Analytical Methodology for Evaluation of the Presence of Esters of Chloropropanol in Foodstuff” 7 Dr. Miguel A. Correa Duarte
Prof. Titular de Química Física Universidade de Vigo Ani Ozcelik
UVIGO
Jorge Antonio Custodio Mendoza
USC
18:10‐18:15 CF16 “Synthetic approach to natural compound thelepamide” 18:15‐18:20 CF17 “Synthesis of natural products with potential biological activity” Ramón Eduardo Millán Álvarez
UDC
Fátima Garrido Fernández
UVIGO
PROGRAMA Viernes, 10 de junio de 2016 MAÑANA 10:00‐10:45 IL5 "NUEVAS PERSPECTIVAS EN RESONANCIA MAGNÉTICA NUCLEAR" 10:45‐10:50 CF18 “Characterization and quantification of copper nanoparticles using single particle inductively coupled plasma‐mass spectrometry (SP‐ICP‐MS)” 10:50‐10:55 CF19 “Palladium and ruthenium compounds derived from polydentate ligands” 10:55‐11:00 CF20 “Bisthiosemicarbazone and thiocarbohydrazide ligands as precursors of helical and meso‐helical architectures” Dr. Teodor Parella Coll
Director del Servei Ressonància Magnètica Nuclear
Universitat Autònoma de Barcelona
Beatriz Esperón Baúlo
USC Patricia María Gaudino Martínez
UDC
Sandra Fernández Fariña
USC
11:00‐11:05 CF21 “A new procedure for the preparation of ε‐
caprolactam and synthesis of ionic liquids for different applications” 11:05‐11:10 CF22 “Metal‐directed self‐sorting of functionalized bipyridinium‐based ligands” Verónica Fernández Stefanuto
UVIGO
11:10‐11:15 CF23 “Exploring the chemical and functional space of DNA‐binding metallopeptide cylinders” Jacobo Gómez González
USC
11:30‐12:00 12:00‐12:45 IL6 Arturo Blanco Gómez
UDC
Café “ESPECTROSCOPIA RAMAN EN MATERIALES PARA ELECTRÓNICA ORGÁNICA” 12:45‐12:50 CF24 “Detection of cations in aqueous medium by surface‐enhanced Raman scattering spectroscopy” 8 Dr. Juan T. López Navarrete
Catedrático de Química Física Universidad de Málaga
Alberto Conde Valiño
UVIGO
12:50‐12:55 CF25 “Extraction and determination of selenium and its species in Brazil nuts (edible nut)” Adriana Mañana López
UDC
12:55‐13:00 CF26 “Detection and quantification of toxins involved in ciguatera fish poisoning (CFP) in UE by LC/MS and comparison with the mouse neuroblastoma assay” David Miguel Castro Alonso
UVIGO
13:00‐13:05 CF27 “Post‐run screening of lipophilic chlorinated pollutants in sludge from urban sewage treatment plants” Mario Roca Fernández
USC
13:05‐13:10 CF28 “Pendant position effects on polyphenylacetilenes” Juan Luis Oubiña Allo
USC
13:10‐13:15 CF29 “Synthesis and reactivity of stannyl and germyl complexes of ruthenium” Nuria María Álvarez Pazos
UVIGO
13:15‐13:20 CF30 “Bioorthogonal Chemistry of Copper (I) inside living cells” Joan Miguel Ávila
USC
13:20‐13:25 CF31 “Synthesis and Characterization of Macrocyclic Ligands and their Metallic Complexes” 13:30‐15:30 Laura Caneda Martínez
UDC
Comida TARDE 15:30‐16:15 IL7 “AVANCES EN FUENTES DE IONIZACIÓN DE PLASMA Y ANALIZADORES DE MASAS INNOVADORES PARA ESPECIACIÓN QUÍMICA MULTIDISCIPLINAR” 16:15‐16:20 CF32 “Rhenium(I) complexes as 99mTc surrogates for estrogen receptor imaging” 16:20‐16:25 CF33 “Synthesis of Dendrimers by Azide‐Alkyne Cycloaddition” 16:25‐16:30 CF34 “Synthesis and Characterization of Ammonium Salts based on Cromoglicic Acid” 16:30‐17:15 17:15‐17:30 IL8 “QUÍMICA Y NANOMEDICINA: BIOPOLÍMEROS Y DENDRÍMEROS PARA TRANSPORTE DE FÁRMACOS Y TERAPIA GÉNICA” CLAUSURA 9 Dr. Alfredo Sanz‐Medel
Catedrático de Química Analítica
Universidad de Oviedo
Saray Argibay Otero
UVIGO
Ágata Millán García
USC
Fernán Berride García
UVIGO
Dr. Ricardo Riguera Vega
Catedrático de Química Orgánica
Universidade de Santiago de Compostela
Comité Organizador Responsables de los seminarios en cada Universidad UDC Coordinador Organizador del Minisimposio:  Dr. Carlos Jiménez González (Coordinador del Máster en la UDC) Secretario del Minisimposio:  Dr. Jaime Rodríguez González (Coordinador del CICA) USC  Dr. Ramón Estévez Cabanas (Coordinador General del Máster)  Dra. Elisa Rubí Cano (Coordinadora de Seminario de Máster) UVigo  Dr. José M. Hermida‐Ramón (Departamento de Química Física de la Universidade de Vigo)  Dra. María Beatriz Iglesias Antelo (Departamento de Química Orgánica de la Universidade de Vigo) 10 MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL
Comité Científico USC  Dr. Ramón Estévez Cabanas (Coordinador General del Máster)  Dr. Víctor Sánchez Pedregal (Departamento de Química Orgánica de la Universidade de Santiago de Compostela) UDC  Dr. Luis A. Sarandeses Dacosta (Departamento de Química Fundamental de la Universidade da Coruña)  Dr. Jesús José Fernández Sánchez (Departamento de Química Fundamental de la Universidade da Coruña) UVigo  Dr. José M. Hermida‐Ramón (Departamento de Química Física de la Universidade de Vigo)  Dra. María Beatriz Iglesias Antelo (Departamento de Química Orgánica de la Universidade de Vigo) 11 MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL
Conferencias invitadas (IL) 1. Dr. José Antonio Salas Fernández
2. Dr. Carlos Platas Iglesias
3. Dr. Emilio Palomares
4. Dr. Miguel A. Correa Duarte
5. Dr. Teodor Parella Coll
6. Dr. Juan Teodomiro López Navarrete
7. Dr. Alfredo Sanz‐Medel
8. Dr. Ricardo Riguera Vega
12 MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL
IL1. Combinatorial biosynthesis and generation of novel bioactive
compounds in actinomycetes
José Antonio Salas
Departamento Biología Funcional e Instituto Universitario de Oncología del Principado de
Asturias (IUOPA). Universidad de Oviedo
[email protected]
Natural products are an important source of bioactive compounds usually isolated from plants,
animals or microorganisms. Microorganisms are producers of a large variety of biologically active
natural products, many of which have clinical, veterinary or agricultural applications. Within
microorganisms, actinomycetes are the most prolific microbial group in terms of production of
bioactive compounds, being producers of approximately two-thirds of all bioactive compounds.
Important and useful therapeutic drugs as antibiotics, antifungals, antiparasites or antitumor drugs
and also compounds with application in agriculture such as insecticides or herbicides are produced
by members of the actinomycetes family. Traditionally, pharmaceutical companies have developed
screening programmes in the search for novel bioactive natural products and improving in production
yields has been based on mutagenesis and selection programmes. The development of recombinant
DNA and its application to actinomycetes has opened up the possibility of applying genetic
manipulation to engineer biosynthetic pathways in order to generate novel derivatives with potential
applications. Thus, “combinatorial biosynthesis” has emerged as a new technology in which genes
from different biosynthetic pathways are combined either in a producer organism or in a heterologous
host1-2. The recombinant strains, containing gene combinations “not previously found in nature”, can
produce novel derivatives from known bioactive compounds. This technology is especially useful
when trying to introduce chemical modifications in bioactive compounds which are not amenable to
chemical means. Combinatorial biosynthesis has been applied to compounds belonging to different
families of bioactive natural products including polyketides, nonribosomal peptides,
indolocarbazoles, etc.3 The fact that many natural products are glycosylated makes glycosylation an
interesting target for combinatorial biosynthesis. Sugars usually participate in the molecular
recognition between the bioactive compound and its cellular target. Taking advantage of the
increasing experimental evidence of a certain degree of substrate flexibility of glycosyltransferases
(particularly with respect to the sugar donor), novel glycosylated derivatives can be generated from
natural products4. In this presentation, we will revise the “state of the art” in the field of combinatorial
biosynthesis and several examples will be shown leading to the formation of novel derivatives from
known bioactive compounds.
References
(1)
(2)
(3)
(4)
Olano, C.; Méndez, C.; Salas, J.A. Nat. Prod. Rep. 2009, 26, 628-660.
Olano, C.; Méndez, C.; Salas, J.A. Nat. Prod. Rep. 2010, 27, 571-616.
Sánchez, C.; Zhu, L.; Braña, A.F.; Salas, A.P.; Rohr, J.; Méndez, C.; Salas, J.A. Proc. Natl. Acad. Sci. U.S.A.
2005, 102, 461-466.
Rodríguez, L.; Aguirrezabalaga, I.; Allende, N.; Braña, A.F.; Méndez, C.; Salas J.A. Chem. Biol. 2002, 9, 721729.
IL2. Contrast Agents for Magnetic Resonance Imaging based on
Metallic Complexes
Carlos Platas-Iglesias
Centro de Investigacións Científicas Avanzadas (CICA) and Departamento de Química
Fundamental, Universidade da Coruña, Campus da Zapateira-Rúa da Fraga 10, 15008 A Coruña,
Spain
[email protected]
Lanthanide(III) [Ln3+] complexes stable in aqueous solutions are currently receiving a great deal of
attention due to their important biomedical and bioanalytical applications. For instance, Ln3+
complexes of polyaminocarboxylate ligands based on either macrocyclic or non-macrocyclic
platforms are commonly employed as contrast agents in Magnetic Resonance Imaging (MRI).1 These
contrast agents are typically small paramagnetic Gd3+ chelates that enhance the longitudinal and/or
transverse relaxation rates of water protons.
Complexes of the Ln3+ ions are also the subject
of intense investigation as contrast agents based
on the Chemical Exchange Saturation Transfer
(CEST) approach, which represent an attractive
alternative to the classical Gd3+-based agents.2
CEST agents based on Ln3+ ions typically
contain a pool of exchangeable protons in
intermediate-to-slow condition with the bulk
water (kex  ). Application of a presaturation
pulse at the frequency of the exchangeable
protons (i. e. hydroxyl or amide protons)
provokes the transfer of some saturated spins
into the water pool, thereby attenuating the
signal of bulk water (see Figure 1). Another
attractive alternative to the Gd3+-based contrast
agents is the use of Mn2+ chelates,3 in particular
due to the better toxicity profile of this metal ion
3+
3+
Figure 1. CEST spectrum of a Yb complex. compared with Gd . This lecture will present
Saturation of the resonance due to hydroxyl an overview of the contributions of the author
to develop contrast agents
protons of the ligand at ~40 ppm provokes an and his co-workers
3+
2+
based
on
Gd
,
Mn
and the CEST approach.
attenuation of the bulk water signal (0.0 ppm) of
about 50%.
References
(1)
(2)
(3)
The Chemistry of Contrast Agents in Medical Magnetic Resonance Imaging (Eds: A. E. Merbach, L. Helm, E.
Tóth), Second Edition, Wiley, New York, 2013.
Viswanathan, S. J. Ratnakar, K. N. Green, Z. Kovacs, L. M. De León-Rodríguez, A. D. Sherry, Angew. Chem.
Int. Ed., 2009, 48, 9330-9333.
M. Regueiro-Figueroa, G. A. Rolla, D. Esteban-Gómez, A. de Blas, A. de Blas, T. Rodríguez-Blas, M. Botta, C.
Platas-Iglesias, Chem. Eur. J. 2014, 20, 17300-17305.
IL3. Photo-induced Carrier Recombination Kinetics in Mixed Halide
Perovskite Solar Cells
Emilio J. Palomares1,2
1
Institute of Chemical Research of Catalonia (ICIQ). Avda. Països Catalans, 16. Tarragona.
E-43007. Spain
2
ICREA. Passeig Lluís Companys, 23. Barcelona. E-08010. Spain
[email protected]
During my lecture I will present our latest results on the characterization of different type of devices
that include MAPI as light harvesting material using advanced photo-induced time resolved
techniques1-4. Using PICE (Photo-induced charge extraction), PIT-PV (Photo-induced Transient
PhotoVoltage) and other techniques, we have been able to distinguish between capacitive electronic
charge, and a larger amount of charge due to the intrinsic properties of the perovskite material.
Moreover, the results allow us to compare different materials, used as hole transport materials
(HTM), and the relationship between their HOMO and LUMO energy levels, the solar cell efficiency
and the charge losses due to interfacial charge recombination processes occurring at the device under
illumination. These techniques and the measurements carried out are key to understand the device
function and improve further the efficiency and stability on perovskite MAPI based solar cells.
Figure.1 Measured charge in complete devices (left) using PIDC ( Photo Induced Differential Charging) and the
measured PIT-PV ( Photo Induced Transient Photovoltage) decays for two solar cells with different TiO2/MAPI
interface.
References
(1)
(2)
(3)
(4)
Marin-Beloqui, J. M.; Lanzetta, L.; Palomares, E. Decreasing Charge Losses in Perovskite Solar Cells Through
mp-TiO2/MAPI Interface Engineering. Chem. Mater. 2016, 28, 207-213.
O'Regan, B. C.; Barnes, P. R. F.; Li, X.; Law, C.; Palomares, E.; Marin-Beloqui, J. M. Optoelectronic Studies
of Methylammonium Lead Iodide Perovskite Solar Cells with Mesoporous TiO2: Separation of Electronic and
Chemical Charge Storage, Understanding Two Recombination Lifetimes, and the Evolution of Band Offsets
during J-V Hysteresis. J. Am. Chem. Soc. 2015, 137, 5087-5099.
Matas Adams, A.; Marin-Beloqui, J. M.; Stoica, G.; Palomares, E. The influence of the mesoporous TiO2
scaffold on the performance of methyl ammonium lead iodide (MAPI) perovskite solar cells: charge injection,
charge recombination and solar cell efficiency relationship. J. Mater. Chem. A 2015, 3, 22154-22161.
Cabau, L.; Garcia-Benito, I.; Molina-Ontoria, A.; Montcada, N. F.; Martin, N.; Vidal-Ferran, A.; Palomares, E.
Diarylamino-substituted tetraarylethene (TAE) as an efficient and robust hole transport material for 11%
methyl ammonium lead iodide perovskite solar cells. Chem. Commun. (Cambridge, U. K.) 2015, 51, 1398013982.
IL4. Hierarchical Plasmonic Nanostructured Materials: Synthesis and
Applications
Miguel A. Correa-Duarte
Department of Physical Chemistry, Biomedical Research Center (CINBIO), and Institute of
Biomedical Research of Ourense-Pontevedra-Vigo (IBI), Universidade de Vigo, 36310 Vigo, Spain
[email protected]
In the near future, hierarchically organized plasmonic nanostructured materials holding multiple
functionalities, are expected to play a key role in many different fields, such as drug delivery, optics,
catalysis, or sensing, among others. However, there is still an important lack of knowledge with
regard to their fabrication which in the end, limits their applicability in the areas of interest. We report
herein the implementation of novel strategies for the fabrication of such materials based on the
confinement of plasmon-resonant nanoparticles. In a first example, the ability of plasmonic
nanoparticles to concentrate light at the nanometer scale has been exploited for the simultaneous
thermal activation and optical monitoring of high energy-demanding chemical reactions. As a proof
of concept, a Diels-Alder cycloaddition reaction has been carried out into the inner cavities of
plasmonic nanocapsules in order to evidence their efficacy as nanoreactors. Thus, it is demonstrated
that this process can be performed in a confined volume with no alteration of the temperature of the
bulk solvent, allowing at the same time a real time monitoring of the reaction progress. These
plasmonic nanostructures have been also shown to be efficient nanoprobes for relevant signaling
molecules. In this regard, an advanced hybrid SERS sensor has been implemented so as to perform
the intracellular detection of NO. With this aim, a NO- chemoreceptor functionalization of plasmonic
nanoparticles has been performed in order to engineer a quantitative fully biocompatible sensor
capable of executing an in situ real time monitoring of the dynamics of NO in living cells. This
sophisticated design prevents the interaction of cytosolic macromolecules with the active optical
material and the enzymatic degradation of the sensing elements. Finally, anisotropic plasmonic
nanoparticles with hot spots in Au-metal oxide hierarchical nanoarchitectures is discussed for
enhancing hot electron-driven photocatalysis, as well as infrared shielding.
References
(1)
(2)
(3)
Vázquez-Vázquez, C., Vaz, B., Giannini, V., Pérez-Lorenzo, M., Álvarez-Puebla, R. A. and Correa-Duarte, M.
A.“ Nanoreactors for Simultaneous Remote Thermal Activation and Optical Monitoring of Chemical
Reactions,” J. Am. Chem. Soc. 2013, 135, 13616–13619.
Rivera-Gil, P, Vázquez-Vázquez, C., Giannini, V., Callao, M. P., Parak, W. J., Correa-Duarte, M. A. and
Álvarez-Puebla, R. A., “Plasmonic Nanoprobes for Real-Time Optical Monitoring of Nitric Oxide inside Living
Cells,” Angew. Chem. Int. Ed. 2013, 52, 13694–13698.
Pérez-Lorenzo, M., Vaz, B., Salgueiriño,V. and Correa-Duarte,M. A, “Hollow-Shelled Nanoreactors Endowed
with High Catalytic Activity,” Chem. Eur. J. 2013, 19, 12196–12211.
IL5. New perspectives in Liquid-State NMR Spectroscopy
Teodor Parella
Servei de Ressonància Magnètica Nuclear, Universitat Autònoma de Barcelona, E-08193
Bellaterra, (Barcelona) Catalonia.
[email protected]
Sensitivity and resolution are the two key points that are always under development in high-resolution
NMR spectroscopy. I would like to present some modern approaches, most of them based on old
ideas, which we are currently developing and running in our NMR facility. The main objective of this
talk is to provide a general overview of new methods that can become perfect complements to regular
NMR experiments that are routinely performed in NMR labs.
The pure-shift NMR concept will be introduced as a tool to remove the J(HH) multiplicity coupling
patterns and to minimize signal overlap in 1H NMR spectra 1. Some discussions about the current
pros and cons of these techniques will be discussed and several chemical applications illustrating the
advantages to obtain highly resolved homodecoupled 1H NMR spectra will be presented.
At the same time, i) new NMR experiments to trace out ultra-long-range correlations2 and to quantify
the magnitude and the sign of heteronuclear coupling constants3, ii) the use of Residual Dipolar
Couplings (RDCs) to obtain long-distance orientational information as alternative to the known NOE
effect and iii) the basic principles of DOSY experiments tocharacterizemolecularsizes4 will be
also commented.
References
(1)
(2)
(3)
(4)
a) Castañar, L. and Parella T. Broadband 1H homodecoupled NMR experiments: Recent developments, methods
and applications. Magn. Reson. Chem. 2015, 53, 399-426. b) Castañar, L. et al. Disentangling complex mixtures
of compounds having near-identical 1H and 13C NMR spectra by pure shift NMR. Chem. Eur. J. 2015, 21, 76827685. c) Marcó, N. et al. Ultra high-resolution HSQC: Application to the efficient and accurate measurement of
heteronuclear coupling constants. Chem. Comm. 2015, 51, 3262-3265. d) Pérez-Trujillo, M. et al. Simultaneous
1
H and 13C NMR enantiodifferentiation from highly resolved pure shift HSQC spectra. Chem. Comm. 2014, 50,
10214-10217.
a) Saurí, J. et al. Homodecoupled 1,1- and 1,n-ADEQUATE: Pivotal NMR Experiments for the structure
revision of cryptospirolepine. Angew. Chem. Intl. Ed. 2015, 54, 10160-10164. b) Williamson, R.T. et al. LRHSQMBC: A sensitivity NMR technique to probe very long-range heteronuclear coupling pathways. J. Org.
Chem. 2014, 79, 3887-3894.
a) Castañar, L. et al. Recent advances in small molecule NMR: Improved HSQC and HSQMBC experiments.
Annual Reports on NMR Spectroscopy, 2015, 84, 163-232. b) Castañar, L. et al. Pure In-Phase heteronuclear
correlation NMR experiments. Angew. Chem. Intl. Ed. 2014, 53, 8379-8382. C) Font. M et al. Direct observation
of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis. Nat. Comm. 2014, 5, 4373.
a) Cabrera-González, J.et al. High boron-content porphyrin-cored aryl-ether dendrimers: controlled synthesis,
characterization and photophysical properties. Inorg. Chem. 2015, 54, 5021-5031. b) García-simón, C. et al.
Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage. J. Am. Chem.
Soc. 2015, 137, 2680-2687. c) García-Simón, C. et al. Sponge-like molecular cage for purification of fullerenes.
Nat. Comm. 2014, 5, 5557.
IL6. Vibrational Raman Shifts and Conjugation: The case of
semiconducting organic materials
Juan T. López Navarrete
Departamento de Química Física, Facultad de Ciencias, Universidad de Málaga, 29071-Málaga
(Spain)
[email protected]
Organic materials have traditionally been considered electrically insulating. This idea, however,
began to change when it was discovered that crystals of phthalocyanine and its derivatives showed
semiconductor character. Twenty-five years later, Heeger, McDiarmid and Shirakawa discovered that
the conductivity of polyacetylene could be modulated from an insulating to a conducting state by
doping with oxidizing agents (1). This marked the initial point for a new interdisciplinary field of
research, nowadays known by the general name of organic electronics. Semiconducting organic
materials have a lot of applications in this new materials field.
The contributions from vibrational spectroscopy (infrared and Raman) to the field of semiconducting
polymers and oligomers are rather unique since vibrational spectra provide simultaneous and
selective information on the conjugative structure and on its charge distribution if pertinent to the
conjugation property. In this seminar, the Raman spectroscopic behavior of molecular materials
characterized by the presence of conjugated pi electrons is discussed. This description will be
accompanied by the illustration of models developed so far in order to account for such spectroscopic
peculiarities (2). Among the pi-conjugated oligomers, oligothiophenes are one of the most versatile
compounds. These materials have rapidly been applied to a wide range of devices, including lightemitting diodes (LEDs), organic field-effect transistors (OFETs) and photovoltaic cells (3).
References
(1)
(2)
(3)
Chiang, C.K.; Druy, M.A.; Gau, S.C.; Heeger, A.J.; Louis, E.J.; MacDiarmid, A.G.; Park, Y.W.; Shirakawa, H.
J. Am. Chem. Soc. 1978, 100, 1013-1015.
Casado, J.; Ponce Ortiz, R.; López Navarrete, J.T. Chem. Soc.Rev. 2012, 41, 5672-5686.
Casado, J.; Pappenfus, T.M.; Miller, L.L.; Mann, K.R.; Ortí, E.; Viruela, P.M., Pou-Amerigo, R.; Hernández,
V.; López Navarrete, J.T J. Am. Chem. Soc. 2003, 125, 2524-2534.
IL7. Advances on plasma ion sources and mass analysers for deeper
insights into chemical speciation and proteomics
Alfredo Sanz-Medel
Department of Physical and Analytical Chemistry, University of Oviedo
[email protected]
The classical boundaries and tools of Atomic Spectrometry are blurring nowadays. Atomic
spectroscopists one day studying photon/atoms interactions, are today investigating also the
molecules constituting their samples (i.e. chemical speciation). On the other hand, more and more
bioscientists are learning to make use of analytical strategies of atomic spectrometry and chemical
speciation (e.g. in proteomics). The outstanding analytical potential of mass spectrometry (MS) is
becoming the chemical ladder to scalate from isotopes, atoms, elements and molecules up to
nanoparticles and nanostructures of matter.
An atmospheric plasma ion source (e.g. ICP) with a mass analyser and an appropriate separation
could form the basis for analysing directly metalloproteins. In any case that elemental speciation
using ICP-MS, should be completed with the corresponding molecular (MALDI- or ESI-MS)
information for “integrated” chemical speciation. These combinations are opening new avenues and
insights in bioscience. Traditionally, the biologically relevant non-metals S and P have been elusive
to sensitive ICP-MS determinations. However, the new ICP(QQQ)MS instruments enable S and P
analysis at very low limits of detection (orders of magnitude better than ICP-MS used before). This
sensitive S and P determinations turns out to be of critical importance to allow direct absolute
quantification of proteins or of protein phosphorylations (by S and P simultaneous determinations)
for targeted proteomics (1).
Also, highly amplified ICP-MS detections can be achieved by tagging the protein of interest with
metal nanoparticles (NPs). The high number of ICP-MS detectable atoms, per NP tag, enables a much
higher sensitivity of the corresponding proteins by metal NPs tagged immunoassays. What is more,
such amplifications can be enhanced by orders of magnitude if we select a special NP (e.g. ZnS(Mn)
QDs) which, by a spontaneous catalytic reduction, deposits on its surface relatively huge amounts of
native gold form a Au(III) proper solution. Subsequent elemental detection of this Au by ICP-MS
allows an ultra-sensitive indirect determination of the NP-tagged protein. We will illustrate the
developed immunoplatform and its extraordinary performance for real-life determinations of
extremely low levels in human serum of “early alarm biomarkers” of cancer (2).
A less known low-pressure plasma-MS instrumental development is the Pulsed Glow DischargeMass Spectrometer (PP-GDMS(TOF)) developed in part in our laboratory. Characteristics and
analytical applications, simultaneous speciation, elemental depth profiling of nm-layered materials
and elemental/molecular screening of polymeric materials will be described. At this moment the first
worldwide commercial PP-GDMS(TOF) is available in our Research Group in Oviedo and its actual
analytical potential for nm-depth profiling and speciation in the solid will be discussed (3).
References
(1)
(2)
(3)
Diez Fernández S., Sugishama N., Ruiz Encinar J., Sanz-Medel A., Anal. Chem. 2012, 84, 5851−5857
García Cortés M., Ruiz Encinar J., Costa-Fernandez J.M., Sanz-Medel A., Biosensors and Bioelectronics (In
press)
Lobo L., Fernandez B., Muñiz R., Pereiro R., Sanz-Medel A.,J. Anal. At. Spectrom., 2016, 31, 212-219
IL8. Chemistry and Nanomedicine: Biopolymers and Dendrimers in
Drug and gene Delivery
Ricardo Riguera
Departamento de Química Orgánica y Centro Singular de Investigación en Química Biológica y
Materiales Moleculares, (CIQUS). Universidad de Santiago de Compostela. ESPAÑA
[email protected]
The selective transportation of small drugs, proteins or nucleic acids to specific target cells, is one of
the main objectives in Nanomedicine and requires the preparation of nanostructures with
demonstrated stability in vivo, low toxicity and immunogenicity.
In this presentation I will show examples of nanosystems based on Biopolymers and on Dendrimers,
that allow the selective delivery of drugs, peptides, proteins and DNA making use of antibodies or
other orienting molecules, to address the drug to the selected target.
The chemistry involved in this work includes, the modification of polysaccharides and dendrimers,
for the introduction of a variety of functions (PEG, sugars, anions, cations, steroids, vitamins,
fluorescent labels, antibodies etc.) designed to improve the stability of the nanostructures in blood, to
allow its visibility in the cells, to facilitate a selective accumulation on the target cells/organs etc.
OH
OH
O
O
HO
O
O
HO
Y
O
O
HO
NHAc
NH
a
O
Antibody
O
Azide for
functionalisation
NH2
b
O
Drug containing
Nanoparticles
OH
c
PEG
O-X
X= N3, FITC
n
Fluorescent
label
Particular attention will be paid to the chemical methods used to prepare the Dendrimers and
Biopolymers, to the procedures for the bioconjugation, particularly the Click reaction, to the
incorporation of the drug by encapsulation or covalent bonding and to ways to liberate the drug inside
the cell. In vitro and in vivo examples of drug and gene delivery will be shown.
References
(1)
(2)
(3)
(4)
(5)
Lallana, E.; Riguera, R.; and Fernandez-Megia, E. Angewandte Chemie Int. Ed. 2011, 50, 8794 – 8804
Lallana, E.; Sousa-Herves, A.; F. Fernandez-Trillo, Riguera, R.; and Fernandez- Megia,E. Pharmaceutical
Research, 2012, 29,1-34 and 902-921
Fernandez-Megia, E; Raviña, M; de la Fuente, M.; Correa, J.; Sousa-Herves, A.; Riguera, R.; Alonso, M.J.;
Sanchez, A. Nanomedicine, 2012, 11 1667-1681
Sousa-Hervés, A.; Novoa-Carballal, R.; Riguera, R.; and Fernandez-Megia, E.; AAPS Journal. 2014, 16,
948-961
Fernandez-Villamarin, M; Sousa-Herves, A.; Correa,J.; Maria Munoz, E.; Taboada, P; Riguera, R. and
Fernandez-Megia, E. ChemNanoMat 2016, DOI: 10.1002/cnma.201600008
Comunicaciones flash (CF) 1. Berta Álvarez Pérez, USC
18. Beatriz Esperón Baúlo, USC
2. María Alejandra Pérez Quintiana,
UDC
19. Patricia María Gaudino Martínez,
UDC
3. Laura Vilas Trigo, UVIGO
20. Sandra Fernández Fariña, USC
4. Ana María Ares Fuentes, USC
21. Verónica Fernández Stefanuto,
UVIGO
5. Verónica Castro Bustelo, USC
22. Arturo Blanco Gómez, UDC
6. Francisco Reigosa Chamorro, USC
23. Jacobo Gómez González, USC
7. Javier Cisneros Sureda, UDC
24. Alberto Conde Valiño, UVIGO
8. Sheila Barrios Esteban, USC
25. Adriana Mañana López, UDC
9. Hugo Santalla García, UVIGO
10. Martín Testa Anta, UVIGO
26. David Miguel Castro Alonso,
UVIGO
11.Julio Corredoira Vázquez, USC
27. Mario Roca Fernández, USC
12. Alicia Prieto Troitiño, UVIGO
28.Juan Luis Oubiña Allo, USC
13. Iago Neira García, UDC
29. Nuria María Álvarez Pazos, UVIGO
14. Ani Ozcelik, UVIGO
30. Joan Miguel Ávila, USC
15. Jorge Antonio Custodio Mendoza,
USC
31. Laura Caneda Martínez, UDC
32. Saray Argibay Otero, UVIGO
16. Ramón Eduardo Millán Álvarez,
UDC
33. Ágata Millán García, USC
17. Fátima Garrido Fernández, UVIGO
34. Fernán Berride García, UVIGO
CF1. Synthesis and reactivity of an aryne precursor derived from
biphenylene
Berta Álvarez, Dolores Pérez, Diego Peña
Departamento de Química Orgánica and Centro Singular de Investigación en Quimica Biolóxica y
Materiais Moleculares (CIQUS), Universidade de Santiago de Compostela, C/Jenaro de la Fuente
s/n, 15782, Santiago de Compostela, España
[email protected]
The synthesis of nanometric aromatic hydrocarbons has sparked renewed interest due to their use as
molecular materials. In recent years our research group has developed simple methods for the
construction of these compounds using aryne chemistry. In particular, the access to graphenic
molecules with trigonal symmetry has been achieved by aryne cyclotrimerization.1 This kind of
nanographenes could be extraordinarily useful for the construction of electronic devices on insulating
or semiconductor surfaces.2
In this context, this project has focused on the preparation of polycyclic aryne precursors containing
a biphenylene moiety, such as triflate 4, and the study of their reactivity. The combination of aromatic
and antiaromatic rings in the resulting molecules is expected to produce significant changes in the
optoelectronic properties that could be used for the development of new functional materials. In this
way, we study the synthesis of aryne 5 starting from biphenylene (1), and its participation in
cycloaddition reactions.
References
(1)
(2)
a) B. Schuler, S. Collazos, L. Gross, G. Meyer, D. Pérez, E. Guitián, D. Peña, Angew. Chem. Int. Ed. 2014, 53,
9004. b) J. M. Alonso, A. E. Díaz-Álvarez, A. Criado, D. Peña, D. Pérez, E. Guitián, Angew. Chem. Int. Ed.
2012, 51, 173.
a) W.-H. Soe, C. Manzano, N. Renaud, P. de Mendoza, A. De Sarkar, F. Ample, M. Hilwa, A. M. Echavarren,
N. Chandrasekhar, C. Joachim, ACS Nano 2011, 5, 1436. b) S. Godlewski, M. Kolmer, M. Engelund, H.
Kawai, R. Zuzak, A. Garcia-Lekue, M. Saeys, A. M. Echavarren, C. Joachim, D. Sanchez-Portal, M.
Szymonskia, Phys. Chem. Chem. Phys., 2016, 18, 3854
CF2. Stereochemistry determination of macrocycles from marine
sponges and synthesis of analogs of the siderophore anguibactin María Alejandra Pérez Quintiana, Jaime Rodríguez González, Carlos Jiménez González
Departamento de Química Fundamental, Facultad de Ciencias y Centro de Investigaciones
Científicas Avanzadas (CICA), Universidad de A Coruña, A Coruña E-15071, España.
[email protected]
This project has two specific goals: the elucidation of the relative stereochemistry of two new
cytotoxic marine natural products and the synthesis of analogs of the natural product anguibactin.
The determination of the relative and absolute configuration of a new compound is one of the most
problematic parts in the process of its structural elucidation1. The first aim of the project is to learn
the most useful NMR techniques to determine the relative stereochemistry of compounds bearing 1,2
and 1,3-substituted chiral acyclic systems by using the J coupling constants conformacional analysis.
In the present work, this method will be applied to the resolution of the relative stereochemistry of
two natural products, which exhibited cytotoxic activities against tumor cells lines, produced by the
marine sponge belonging to Haplosclerida family. The plane structure was deduced by analysis of
mass spectrometry and mono and bidimensional NMR experiments such Edited-HSQC, COSY and
HMBC. The relative stereochemistry will be described using HSQC-HECADE and NOESY
experiments.
O
O
N
S
HO
OH
N
OH
Anguibactin
N
N
N
H
S
iPrO
N
OH
+
O iPr
HN
OBn
N
H
Fragment A
Fragment B
DHBA + L-Serine
Histamine
Scheme 1. Proposed retrosynthetic analysis for anguibactin.
Siderophores are low molecular weighted compounds, which specifically chelate ferric ions, used by
bacteria to grow under low iron conditions.2 Anguibactin is a siderophore produced by Vibrio
anguillarum (serotype O1), a pathogen responsible of vibriosis, a disease which causes severe
economic losses worldwide.3 As a second aim of my project, the approximation of anguibactin will
be presented (see scheme 1).4
References
(1)
(2)
(3)
(4)
Matsumori, N.; Kaneno, D.; Murata, M.; Nakamura, H. J. Org. Chem. 1999, 64, 866–876.
Neilands, J. B. J. Biol. Chem. 1995, 270, 26723–26726.
Frans, I.; Michiels, C. W.; Bossier, P.; Willems, K. A.; Lievens, B.; Rediers, H. J. Fish Dis. 2011, 34, 643–661.
Jalal, F.; Actis, L. A.; Crosas, J. H. J. Am. Chem. Soc. 1999, 111, 292–296.
CF3. Palladium NPs for Arsenic and Antimony speciation followed
analysis by TXRF and sample preparation strategies using
microextraction techniques
Laura Vilas Trigo
Department of Analytical Chemistry and Food, Chemistry Faculty, University of Vigo, Vigo
[email protected]
This final master work consists in the synthesis of Pd nanoparticles (NPs) using Pd NO
as metal
precursor and ethanol:water mixture as reducing agent. After synthesis, the NPs are immobilized on
quartz substrates using silanization strategy. Thus, NPs are immobilized and a thin and stable
nanoparticulate layer is obtained1. It is known that Pd NPs have catalytic activity and can be used for
the decomposition of covalent hydrides, e.g. arsine (AsH3) and stibine (SbH3), at room temperature.
These volatile hydrides are generated by means of a continuous flow system and flushed onto the
immobilized Pd NPs for trapping.
After preconcentration, Ga (1 mg L-1) is added as internal standard and the quartz substrate is directly
placed on the sample changer for direct total reflection X-ray fluorescence (TXRF) analysis without
further sample preparation. For selective extraction of trivalent arsenic [As(III)] sample solution is
buffered using citrate buffer (pH 4.5). For total As and Sb determination a mixture ascorbic
acid/potassium iodide (1.25/0.25 % m/v) is used a pre-reducing agent2.
In academic practices, different microextraction techniques were used for sample preparation,
including, single-drop microextraction (SDME)3, ultrasound assisted extraction (UAE)4 and
suspended droplet microextraction (DSDME)5. These techniques were coupled to different analytical
techniques, i.e. UV-Vis micro-spectrophotometry, electrothermal atomic absorption spectrometry
(ETAAS) and fluorospectrometry for the analysis of iodine, cadmium, polycyclic aromatic
hydrocarbons (PAHs) and nitrites in water samples. Besides, direct measurement of solid slurries,
e.g. biological matrices, using TXRF was performed.
References
(1)
(2)
(3)
(4)
(5)
Romero, V.; Costas-Mora, I.; Lavilla, I.; Bendicho, C. Nanoscale. 2015, 7, 1994-2002.
Cava-Montesinos, P.; De la Guardia, A.; Teutsch, C.; Cervera, M.L.; De la Guardia, M. Anal. Chim. Acta. 2003,
493, 195-203.
Pena-Pereira, F.; Lavilla, I.; Bendicho, C. Anal. Chim. Acta. 2009, 631, 223-228.
Capelo, J.L.; Lavilla, I.; Bendicho, C. J. Anal. At. Spectrom. 1998, 13, 1285-1290.
Pena-Pereira, F.; Costas-Mora, I.; Lavilla, I.; Bendicho, C. Talanta. 2012, 89, 217-222.
CF4. Micro-extraction techniques applied to biological samples of
toxicological interest
Ana María Ares Fuentes
Department of Analytical Chemistry. Faculty of Chemistry. University of Santiago de Compostela,
Avda. de las Ciencias, s/n. 15782-Santiago de Compostela, Spain
[email protected]
Illicit drug consumption affects all modern societies. According to the Annual Report of the European
Monitoring Center for Drugs and Drug Addiction1, this consumption continues to increase amongst
Europeans. Apart from classic drugs such cocaine, morphine or heroine, there is a progressive
popularization of the novel psychoactive substances (NPs), which are synthesized from the
amphetamines.
Because of the growing problem of the abuse of these psychoactive drugs2, it is necessary the
development of analytical methods specifically designed to detect this substances in biological
samples such as oral fluid or plasma.
Sample preparation is an important step in separation and determination of compounds of interest
from complex matrices. In the last years, there is an evolution towards the miniaturization of some
techniques. Therefore there have been a number of new micro-extraction procedures, such as solid
phase micro-extraction (SPME), dispersive liquid-liquid micro-extraction (DLLME) and microextraction by packed sorbents (MEPS)3.
The aim of the master thesis is the development and validation of analytical methodology, based in
UPLC-PDA-MS/MS, for the identification and determination of 21 psychoactive substances in oral
fluid using a novel micro extraction technique, named MEPS. The factors which might influence the
extraction are studied previously using the experimental design approach. NemrodW® statistical
software was used for the experimental design generation, for the evaluation of the experimental data
and to plot effects and response surfaces.
In academic practice, two new micro-extraction techniques was used to isolate different drugs of
abuse in different biological matrix. The first technique is the MEPS, which is applied to real plasma
samples for determination of classic drugs of abuse. The second technique is DLLME used in a
method for determination of antidepressants in plasma4. Under optimized conditions the proposed
methods were validated in terms of selectivity, linearity, limits of detection (LOD) and quantification
(LOQ), precision and accuracy, using standard addition calibration.
References
(1)
(2)
(3)
(4)
The state of the drugs problem in Europe. Annual Report; EMCDDA, 2008.
World Drug Report 2015; UNODC, 2015
Ocaña-Gonzalez, J. A.; Fernandez-Torres, R.; Bello-Lopez, M. A. Ramos-Payan, M. Anal Chim Acta. 2016,
905, 8-23.
Fernandez, P.; Taboada, V.; Regenjo, M.; Morales, L.; Alvarez, I.; Carro, A. M.; Lorenzo, R. A. J Pharm
Biomed. Anal. 2016, 124, 189-197. 25 MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL
CF5. Development of a Ultra-High Performance Chromatography
(UHPLC) coupled to tandem MS method for simultaneous
determination of pharmaceuticals and drugs in water samples
Castro Bustelo, Verónica; Quintana Álvarez, José Benito; Rodil Rodríguez, Mª Rosario
Department of Analytical Chemistry, Nutrition and Food Sciences, Group of Chromatography and
Chemometrics (ChromChem), Faculty of Chemistry, University of Santiago de Compostela
[email protected]
Drugs and pharmaceuticals abuse are a global problem with significant direct or indirect adverse
impacts on human health and social welfare. Traditionally, consumption measurement is evaluated
by surveys which are initially processed at national level to establish the prevalence of consumption.
However, the main drawback of this approximation is slowness and reliability of information, since
people tends to lie some cases.
Determination of drugs and its metabolites concentration in environment in water is an indirect tool
to estimate the community level consumption of illicit drug and to evaluate potential ecotoxicological
impacts. The disposal or excretion of products of illicit drugs consumed in a given area is mainly into
local wastewater (1). This detection of illicit drug residues in wastewater can provide evidence-based
real-time information on the nature and magnitude of community-wide illicit drug use.
In this context, ultra-high performance liquid chromatography (UHPLC) coupled to tandem MS
provides an interesting tool for fast determination of these compounds in water samples. Therefore,
the aim of this study was develop a method based on UHPLC-MS/MS for the determination of 41
compounds (pharmaceuticals, drugs and their metabolites) in wastewater.
References
(1)
Castiglioni S, Zuccato E, Chiabrando C, Faneli R, Bagnati R. Detecting illicit drugs and metabolites in
wastewater using high performance liquid chromatography-tandem mass spectrometry. Spectroscopy Europe
2007, 19, 7–9.
CF6. Preparation and characterization of functionalized palladium
complexes
Francisco Reigosa Chamorro
Departamento de Química Inorgánica, Facultad de Química, Universidad de Santiago de
Compostela, Santiago de Compostela.
[email protected]
Our group has carried out several studies related to compounds based on palladium, platinum and
other transition metals.1 These studies included the synthesis and characterization of cyclometallated
compounds as well as their application as catalysts in cross-coupling reactions such as the well-known
Suzuki reaction.
Thiosemicarbazone ligands present a great coordinative capacity due to their potentially donor atoms,
giving way to different types of coordination.2-3 In addition, these molecules allow the
functionalization of the cyclometallated compounds.
In this communication, we report the design, synthesis, characterization and reactivity of a series of
compounds including the boronic acid function. Organometallic compounds were obtained by the
corresponding syntheses and their reactivity against phosphines was tested.
The final compounds were used as catalysts in the Suzuki reaction.
B(OH)2
B(OH)2
N
N
N
N
H
S
NHR 1
B(OH)2
Pd
S
NHR1
4
N
N
Pd
PPh 3
S
NHR 1
References
(1)
(2)
(3)
Martínez, J.; Pereira, M. T.; Ortigueira, J. M.; Bermúdez, B.; Antelo, J. M.; Fernández, A.; Vila, J. M.;
Polyhedron, 2012, 31, 217.
Weiss, H.; Mohr, F.; J. Organomet. Chem. 2011, 696, 3150.
Paul, P.; Datta, S.; Halder, S.; Acharyya, R.; Basuli, F.; Butcher, R. J.; Peng, S.-M.; Lee, G.-H.; Castiñeiras, A.;
Drew, M. G. B.; Bhattacharya, S.; J. Mol. Catal. A: Chem. 2011, 344, 62
CF7. Preparation of magnetic nanoparticles-siderophores conjugates,
and its possible application in pathogen detection.
Javier Cisneros Sureda, Socorro Castro García, Carlos Jiménez González
Departamento de Química Fundamental, Facultad de Ciencias y Centro de Investigaciones
Científicas Avanzadas (CICA), Universidad de A Coruña, A Coruña E-15071, España.
[email protected]
Iron acquisition process is fundamental for the viability of most organisms, because it is involved in
essential biological phenomena like oxygen transport, electron transfer and DNA synthesis. However,
Fe(III) is a biologically limiting element due to its low solubility (10-18M) at neutral pH in aerobic
environments. To overcome this difficulty, most bacteria produce siderophores, low molecular
weight iron chelating agents with extraordinarily high affinity and selectivity for Fe(III).
Siderophores are excreted to the environment to form Fe-complexes, which are internalized trough
specific protein membrane receptors1.
Interaction between Fe-siderophore complexes and membrane receptors is one of the most promising
choices to develop new pathogen detection methods. In this way, we are planning to couple
siderophores to magnetic nanoparticles (MNP) through a linker, with the aim to achieve faster
extraction times and better sensibility. Similar strategies have been reported, such as siderophores
attached to gold surfaces2, and MNP functionalized with monosaccharides3.
SiO2
O
Fe 3O4 O Si
O
O
H
N
N Siderophore analogous
H
O
Figure 1 Siderophore conjugated with magnetic nanoparticles
In the present work, we have synthesized core-shell MNP of magnetite (Fe3O4) with 2 different
silica-coatings, normal and mesoporous SiO2, and functionalized the core-shells systems with an
amine group by addition of 3-aminopropyltriethoxysilane (APTES). Then, ferrioxamine siderophore
(or other analogous) was linked to the amine group through a succinic group or other linkers. All
MNP, siderophores analogous, and conjugates were characterized by different techniques, such as
XRPD, IR, TEM, TGA, NMR and MS. Finally, bacterial culture essays were carried out to evaluate
the effectivity of the method in the development of bacterial detection applications.
During this work, I have improved my experience in the research and update of related bibliography,
organic and nanoparticle synthesis, and employment of characterization techniques cited before.
References
(1)
(2)
(3)
Zheng, T.; Nolan, E. M. Metallomics 2012, 866–880.
Inomata, T.; Tanabashi, H.; Funahashi, Y.; Ozawa, T.; Masuda, H. Dalton Trans. 2013, 42, 16043–16048.
El-boubbou, K.; Gruden, C.; Huang, X. J. Am. Chem. Soc. 2007, 1–26.
CF8. Expression of recombinant proteins in C6/36 mosquito cells
(Aedes Albopictus)
Barrios Esteban, Sheila
José Manuel Martínez Costas (Centro Singular de Investigación en Química Biolóxica e Materiais
Moleculares (CIQUS) and Departamento de Bioquímica e Bioloxía Molecular, Universidade de
Santiago de Compostela), Santiago de Compostela.
[email protected];[email protected]
Based on the viral protein muNS, that constructs the matrix of the avian reovirus viroplasms, we have
developed a molecular tagging methodology named IC-Tagging1,2. Between the many different uses
of our method, a particularity remarkable one is the easy generation of effective subunit vaccines.
Recently, we have adapted the IC-Tagging to the endoplasmic reticulum (ER) environment, where
all the protein posttranslational modifications are carried out. One of the main goals in our lab at the
moment resides in the design and production of subunit vaccines against enveloped viruses that
acquire ER-glycosylated proteins in their outer, cytoplasmic membrane-derived, lipid envelope.
Subunit vaccines against enveloped viruses are very difficult to accomplish with other methods for
vaccine production, but we strongly believe that will be feasible with IC-Tagging3.
Figure 1. Analysis by immunofluorescence of cytoplasmic inclusions containing IC-Tagging.
Aedes albopictus is a mosquito responsible for the transmission of many diseases caused by
enveloped viruses, such as Dengue virus or RVFV (Rift Valley Fever Virus), for many of which there
is not a cure or an effective vaccine. Researches use C6/36 cells (from Aedes Albopictus) to grow
such viruses in the laboratory to high titers, showing that C6/36 cells are able to correctly perform all
the viral. Protein post-translational modifications, what converts these cells in ideal candidates for
the production of subunit vaccines, generated by the IC-Tagging system against these viruses.
As there are not bibliographic data about protein expression in these cell, we decided to test and
compare different methods of protein expression to try adapt the IC-Tagging system to C6/36.
The academic practices, were carried out in a mixed way. On the one hand, the objective is to find
acquire practice in handling different methods of protein expression analysis by immunofluorescence,
Western-blot and learning how to design the construction of recombinant proteins. On the other hand,
the objective is the extraction and determination by UV-VIS spectrophotometry of active and reserve
carbohydrates from different plan tissues of pine species.
References
(1)
(2)
(3)
Plos One 5(11): e13785. Doi: 10.1371/journal.pone.0013785.
Plos One 5(11): e13961. Doi: 10.1371/journal.pone.0013961.
Marín-López, A.; Otero-Romero, I.; de la Poza, F.; Menaya-Vargas, R.; Calvo-Pinilla, E.; Benavente, J.;
Martínez-Costas, J.M.; Ortego, J. Antiviral Research. 2014, 110, 42-51.
CF9. Obtaining epimers of second generation vitamin D analogs
Hugo Santalla García
Departament of Organic Chemistry, University of Vigo, Vigo, Spain, 36210
[email protected]
The 1α,25-(OH)2-vitamin D3 has antiproliferative properties and could be used as a therapeutic agent.
However, the necessary therapeutic doses involve hypercalcemia1 risk. Research focuses on the
rational design of new calcitriol analogs with higher selectivity. The so called second generation
analogs, with side chain modification.
This work is focused on the design of a common pathway for obtaining epimers at the C-20 position
of vitamin D second generation analogs. From the route initially designed for the obtainment of
Gemini2 type analogs, the desired epimer’s structure can be reached by the reduction of hydroxyl
group C-22 position of compound 3, as shown on the scheme.
Second generation analogs, some of which are marketed as drugs can provide interesting
improvements over pharmacological and pharmacokinetic properties of the original analogue, simply
epimerization of C-20.
One of the reactions of this pathway consists in the hydrogenation of two olefins, obtaining a lower
yield than expected due to the dehydration of a tertiary alcohol. To improve yield, the synthesis of a
homogeneous iridium catalyst, specifically Crabtree3 catalyst, and subsequent utilization is
proposed4.
References
(1)
(2)
(3)
(4)
(a), Jones, G.; Strugnell, S. A.; DeLuca, H. F. Physiol. Rev. 1998, 78, 1193. (b) DeLuca, H. F.; Zeierld, C. Nutr.
Rev. 1998, 56, 54. (d) Bouillon, R.; Okamura, W. H.; Norman, A. W. Endocr. Rev. 1995, 16, 200.
Pazos, G. Tesis Doctoral. Universidad de Vigo 2011, 115-163.
Crabtree, R. H.; Morehouse S. M. Inorganic Synthesis 1986, 24, 173-176.
Crabtree, R. H.; Davis, M. W. J. Org. Chem. 1986, 51, 2655-2661.
CF10. Ferrimagnetic CoFe2O4 and antiferromagnetic Cr2O3
nanostructured composites
Martín Testa Anta
Department of Applied Physics, Faculty of Chemistry, University of Vigo, 36310 Vigo
[email protected]
Monodisperse ferrimagnetic CoFe2O4 nanoparticles can be synthesized following the thermal
decomposition of iron(III) acetylacetonate and cobalt(II) acetylacetonate1. On the other hand,
antiferromagnetic Cr2O3 nanoparticles can be prepared by calcination of chromium(III) hydroxide,
which was previously obtained by precipitation of the corresponding nitrate in basic medium2.
A thorough characterization of these nanoparticles was carried out, with a particular emphasis on
Raman spectroscopy. CoFe2O4 and Cr2O3 nanoparticles adopt a spinel and corundum structure
respectively, so by studying the Raman active vibrational modes of these lattices we can obtain
information about their crystalline structure3-4.
Once synthesized, these two types of nanoparticles can be assembled into a nanostructured composite,
on which promoting the exchange bias effect, that is, having both the ferri- and antiferromagnetic
orders of the two oxides coupled.
Figure 1. Diagram showing the exchange bias effect in a FiM-AFM interface
This phenomenon has many applications, particularly in spintronics, since it can be used to pin the
magnetization of a FM or FiM material in a fixed direction of space.
References
(1)
(2)
(3)
(4)
Sun, S.; Zeng, H.; Robinson, D. B.; Raoux, S.; Rice, P. M.; Wang, S. X.; Li, G. J. Am. Chem. Soc. 2004, 126,
273-279.
Bañobre-López, M.; Vázquez-Vázquez, C.; Rivas, J.; López-Quintela, M. A. Nanotechnology 2003, 14,
318-322.
Shebanova, O. N.; Lazor, P. J. Solid State Chem. 2003, 174, 424-430.
Mougin, J.; Le Bihan, T.; Lucazeau, G. J. Phys. Chem. Solids 2001, 62, 553-563.
CF11. A Novel ZnDy Single Molecular Magnet
Julio Corredoira, Matilde Fondo, Jesús Sanmartín Ana M. García-Deibe
Departamento de Química Inorgánica, Facultade de Química, Universidade de Santiago de
Compostela, 15782 Santiago de Compostela. Spain.
[email protected]
Lanthanide containing single-molecule magnets (SMMs) have received much attention in the last
years, as they appear to be the best candidates in the field of molecular magnetism for application in
high density data storage, molecular spintronics and quantum processing.1-2 The advantages of 4f
elements stem from their inherent large magnetic anisotropy and high ground state spin, thus fulfilling
two of the mandatory requirements for an SMM.3
Following with our work in the field of molecular magnetism, here we report the new SMM
{[ZnDy(HL)(NO3)(OAc)(CH3OH)](NO3)}·1.25CH3OH·0.25H2O (1·1.25CH3OH·0.25H2O), which
has been obtained as shown in Fig. 1.
+
Br
H 3CO
OCH 3
OH
OH
N
N
N
HO
OCH 3 Zn(OAc) 2 .2H2 O
Dy(NO3 )3 .XH2 O
N
CH3 OH/CHCl3
Br
Br
H 3L
1
Fig. 1. H3L and reaction scheme, showing the ellipsoid diagram for 1. Color code: N, blue; O, red;
C, gray. Hydrogen atoms and the NO3- counteranion have been omitted for clarity.
Complex 1 consist of [ZnDy(HL)(NO3)(OAc)(CH3OH)]+ cations and NO3- anions. In the cation,
Dy(III) is nine-coordinated (O9), with a distorted muffin geometry, triple bridged with the Zn(II)
metal center through two phenolate groups and one exogenous syn-syn acetate. Dynamic ac magnetic
susceptibility measurements for the complex as a function of the temperature under a dc zero field do
not show peaks in in-phase (’) nor in out of-phase (’’) components of the susceptibility. However,
these peaks appear when a small external dc field of 1000 G is applied, in order to fully or partly
suppresses the quantum tunnelling relaxation of the magnetization. Accordingly,
1·1.25CH3OH·0.25H2O presents SMM behavior, with a calculated energy effective barrier Ueff/k of
24.16 K.
References
(1)
(2)
(3)
Winpenny, R. E. P. Nat. Nanotechnol. 2013, 8, 159-160.
Shiddiq, M.; Komijani, D.; Duan, Y.; Gaita-Arino, A.; Coronado, E.; Hill, S. Nature, 2016, 531, 348-351.
Woodruff, D. N.; Winpenny, R. E. P.; Layfield, R. A. Chem. Rev. 2013, 113, 5110–5148.
CF12. Magnetic nanoparticles: dispersive solid phase extraction for
selenium determination by electrothermal atomic adsorption
spectrometry
Alicia Prieto Troitiño
Analytical and Food Chemistry Department, Faculty of Chemistry, University of Vigo, Vigo
[email protected]
Different nanomaterials have many applications such as catalysis, chromatographic separations,
encapsulation of enzymes or drug delivery.
In recent years a variety of nanosorbents such as carbon nanotubes, metal oxides (SiO2, Al2O3, TiO2,
ZrO2, Fe3O4, etc.) and noble metals (Au, Pd, Ag) have been applied for preconcentration of metal
ions1. Nanosorbents show high adsorption capacity, high adsorptive area, low diffusion resistance,
which make them advantageous over conventional adsorbents. In particular, magnetic nanoparticles
(MPs) allow carrying out a separation by using an external magnetic field.
The aim of this Master Thesis project involves the synthesis, characterization and application of a
new nanosorbent to determine trace levels of selenium in water samples by electrothermal atomic
absorption spectrometry. It is expected that the combination of this instrumental technique with
dispersive solid phase extraction using as MPs as adsorbent will enable the determination of selenium
at trace levels2-4. A scheme of the procedure can be shown in Fig. 1.
Fig. 1. Scheme of the determination of the selenium.
In addition to the above mentioned project, academic practices have reinforced the training in
spectroscopic techniques. Specifically, two atomic and two molecular spectrometric techniques were
used. The experiments involved the determination of cadmium in fish samples by electrothermal
atomic absorption spectrometry, iodide in water by micro-volume UV-visible spectrophotometry,
polycyclic aromatic hydrocarbons in water by micro-volume fluorospectrometry and a
multielemental analysis of micro and macronutrient in foods by total reflection X-ray fluorescence.
References
(1)
(2)
(3)
(4)
Rehber, A. Clean 2007, 35, 6, 548 – 557.
Georgia, G.; Aristidis, N. A. Anal. Chim. Acta, 2013, 789, 1– 16.
Stripeikis, J.; Pedro, J.; Bonivardi, A.; Tudino, M. Anal. Chim. Acta, 2004, 502, 99–105.
Herrero Latorre, C.; Barciela García, J.; García Martín, S.; Peña Crecente, R. Anal. Chim. Acta, 2013, 804, 37–
49.
CF13. Self-assembly of exo-functionalized mononuclear Pd(II) and
Pt(II) metallacycles
Iago Neira, O. Domarco, M. D. García, C. Peinador, J.M. Quintela
Departamento de Química Fundamental and Centro de Investigacións Científicas Avanzadas,
Facultade de Ciencias, Universidade da Coruña, E-15071, A Coruña, Spain
[email protected]
In the context of supramolecular chemistry, coordination-driven self-assembly has been established
as an outstanding tool for the preparation of 2D metallacycles and 3D metallacages.1 The topology
of these discrete self-assembled coordination complexes (SCCs), can be easily adjusted by an
appropriate selection of ligands and metal centers, often resulting into hollow molecular receptors
with shapes and sizes modified virtually at will.
Nevertheless, the synthesis à la carte of SCCs, owning completely predesigned and fine-tuned
structural and functional features, is still a distant goal; in part because of the potential interference
on the self-assembly processes between complexly functionalized ligands with multiple coordination
sites.
In this context, following our continuing interest on the development of new metallacycles,2 as well
as the study of those as molecular receptors and building blocks for interlocked architectures, the
research shown herein would be focused on our progress on the development of a post-assembly
protocol for the functionalization of Pt(II)-based mononuclear metallacycles.
N
N
N
Self-assembly
N
H
H2N
N Pt N
N H2
N
N
N3
Pt(en)(NO3)2
H2O

N
N
H
N3
CuAAC
Ligand
synthesis
N
Ascorbic acid
CuSO4·5H2O
H2O
R
Post-assembly
functionalization
N
H2N
N Pt N
N H2
N
N
N
H
N N
N
R
Scheme 1: Intended post-assembly strategy.
The potential practical applications of the intended PtL receptors are manifold, ranging from their
introduction as building blocks for the construction of complex supramolecular interlocked structures
(catenanes, rotaxanes, knots, etc.), the molecular recognition of relevant biological or environmental
analytes, or their use as non-covalent DNA binders.
References
(1)
(2)
Cook, T. R.; Stang, P. J. Chem. Rev. 2015, 115 , 7001.
(a) Peinador, C.; Blanco, V.; García, M. D.; Quintela, J. M. in Molecular Self-Assembly: Advances and Applications (Ed.:
A. D. Q. Li), Pan Stanford Publishing,Singapore, 2012, pp. 351. (b) García, M. D.; Alvariño, C.; López-Vidal, E. M.;
Rama, T.; Peinador, C.; Quintela, J. M. Inorg. Chim. Acta 2014, 417, 27.
CF14. Chiral Frameworks for the Construction of Functional
Surfaces
Ani Ozcelik
Department of Organic Chemistry, Faculty of Chemistry, University of Vigo, Vigo
[email protected]
Chiral surfaces are very promising for catalytic and sensing applications. Such systems could be
achieved by self-assembly of optically active molecules onto achiral substrates.1 Recently, it has been
demonstrated that Chiral Frameworks (CFs) bearing chiral axes are capable of forming surfaceconfined nanostructures orthogonal to the substrate. These Up-standing Chiral Architectures
(UCAs) offer the possibility for further functionalization of the exposed end to adapt to a particular
use. Nevertheless, the instability of these first examples at ambient conditions hampered their
applicability.2
According to the strategy of Self-Assembled Monolayers (SAMs), stable molecule-substrate
interactions are achievable by the incorporation of thiols as the most employed anchoring groups.3
Additionally, allenes as well as spiranes may present axial chirality upon an appropriate substitution.
In particular, diethynylallenes (DEAs) and diethynylspirobifluorenes (DESs) present remarkable
chiroptical responses4 while the latter presents higher stability. Consequently, synthesis of thiolderivatized CFs bearing DEAs and DESs was explored. Furthermore, photo- and thermal-stability
studies were performed via Electronic Circular Dichroism (ECD) spectroscopy. Finally, SAMs of
the synthesized CFs were prepared on semi-transparent Au substrates which led to great enhancement
on the stability of the formed UCAs.
Thiol-derivatized CFs
bearing DEAs
Thiol-derivatized CFs
bearing DESs
Surface Confined
UCAs
Semi-transparent
Au Substrate
References
(1)
(2)
(3)
(4)
Ernst, K. H. Phys. Status Solidi Basic Res. 2012, 249 (11), 2057–2088.
Zhang, Y.-Q.; Öner, M. A.; Lahoz, I. R.; Cirera, B.; Palma, C.-A.; Castro-Fernández, S.; Míguez-Lago, S.; Cid,
M. M.; Barth, J. V.; Alonso-Gómez, J. L.; Klappenberger, F. Chem. Commun. 2014, 50 (95), 15022–15025.
Vericat, C.; Vela, M. E.; Benitez, G.; Carro, P.; Salvarezza, R. C. Chem. Soc. Rev. 2010, 39 (5), 1805–1834.
Castro-Fernández, S.; Cid, M. M.; López, C. S.; Alonso-Gómez, J. L. J. Phys. Chem. A 2015, 119 (9), 1747–
1753.
CF15. Development of Fast Analytical Methodology for Evaluation of
the Presence of Esters of Chloropropanol in Foodstuff
Jorge Antonio Custodio Mendoza, Antonia María Carro Díaz, Rosa Antonia Lorenzo Ferreira
Analytical Chemistry, Nutrition and Bromatology Department, Faculty of Chemistry; USC,
Santiago de Compostela
[email protected]; [email protected]; [email protected]
In food industry quality standards are quite strict, especially with regard to food safety, even thought
current direct method have been validated for determination of a wide range of food contaminant, the
intension is to develop a new method with innovative sample preparation technique in order to
analyze potentially toxic compounds that might impair foodstuff quality.
Glycidyl esters and 3-monochloropropane-1,2-diol mono and di esters, which are generating during
edible oil processing, more specific at deodorizing step of refining process, and domestic preparation
including baking, boiling, frying, grilling and toasting, are contaminants that has been considered to
be carcinogen.1,2
Since there are no toxicological data on 3-MCPD esters its recent risk assessment on toxicological
data on 3-MCPD knowing that it is released from its esters, European Commission Regulation (EC)
Nº466/2001 prescribes maximum levels of 3-MCPD of 0.02mg/kg3.
Glycidyl Ester
3-Chloropropane-1,2-diol
Mono Ester
3-Chloropropane-1,2-diol
Di Ester
This compounds has been extracted from edible oil and the identification and quantifications has been
develop by Liquid Chromatography-Triple Quadrupole Tandem Mass Spectrometry with Electro
Spray Ionization (ESI), the method has been validated for Glycidyl-Palmitate (PA-GE), GlycidylOleate (OL-GE), Palmitoyl-3MCPD (PA), Oleoyl-3MCPD (OL), Oleoyl-Stearoyl-3MCPD (OL-ST),
Oleoyl-Linoleoyl-3MCPD (OL-LI), Dilinoleoyl-3MCPD (LI-LI), Palmitoyl-Linoleoyl-3MCPD
(PA-LI), Dipalmitoyl-3MCPD (PA-PA), y Palmitoyl-Oleoyl-3MCPD (PA-OL) using an internal
standard calibration curve with isotopical labeled compounds.
References
(1)
(2)
(3)
European Food Safety Authority. (2008) Statement of the Scientific Panel on CONTAM on a request from the
EFSA related to 3-MCPD esters. (EFSA-Q-2008-258)
Hamlet, C.G., Asuncion L., Velísek J., Dolezal M., Zelinková Z., Crews C. Formation and occurrence of esters
of 3-chloropropane-1,2-diol (3-CPD) in foods: What we know and what we assume. Eur. J.Lipid Sci. Technol.
113 (2011) 279.
Commission Regulation (EC) No. 1881/2006 19 December 2006 setting maximum levels for certain
contaminants in foodstuffs. Off. J. Eur. Union L364, 5-24.
http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2006:364:0005:0024:EN:PDF (last access, April
2016).
CF16. Synthetic approach to natural compound thelepamide
Ramón Millán Álvarez
Departamento de Química Fundametal, Facultade de Ciencias, Universidade da Coruña, A Coruña
Ramon.e.millan @udc.es
Thelepamide is a metabolite of marine origin which it has been isolated from annelid Thelepus
Crispus. This natural compound presents citotoxic activity in vitro against leukemia tumor cells.1 Its
structural elucidation has been done in 2013 and it has been achieved the determaination of its
structure and its relative stereochemistry.2
OH
3
1
O
7
9
5
S
11
N
OH
O
14
OH
O
16
15
17
Final master thesis is based in the synthetic study of thelepamide. Specifically, the work is focused
on achieving a stereoselective synthetic approach to the carbon skeleton corresponding to C1-C11
fragment. For this, it has been proposed two possible synthetic routes.
One of them is based on performing a stereoselective conjugate addition using a chiral auxiliary.3
O
O
O
O
HS
OMe
NHBoc
N
O
O
S
OMe
H2 N
The other approach is referred to realize a nucleophilic substitution employing as nucleophile an
enantiopure compound with a thiol group with its corresponding preparation.4
O
O
OH
O
O
SH
O
N
O
S
NH 2
OMe
H 2N
References
(1)
(2)
(3)
(4)
Nieto, R. M. Nuevos compuestos de organismos marinos farmacológicamente activos, Tesis Doctoral,
Departamento de Química Fundametal, Universidade da Coruña, A Coruña, 2013.
Rodríguez, J.; Nieto R. M.; Blanco, M.; Valeriote, F. A. ; Jiménez C.; Crews, P. Org. Lett. 2014, 16, 464.
Cagnoli, R.; Lanzi, M.; Mucci, A.; Parenti, F.; Schenettia L. Synthesis 2005, 2, 267–271.
Palomo, C.; Oiarbide, M.; López, R.; González, P.; Gómez-Bengoa, E.;. Saá ,J.M.; Linden, A. J. Am. Chem.
Soc. 2006, 128, 15236-15247.
CF17. Synthesis of natural products with potential biological activity.
Fátima Garrido Fernández
Department of Organic Chemistry, Faculty of Chemistry, University of Vigo, Vigo
[email protected]
One of the most active areas of research in organic synthesis, is the search for new methodologies for
the synthesis of carbocycles and heterocycles, as these constitute the structure of complex molecules
that show a wide range of biological activities. Access to those complex structural moieties from
natural sources is indeed very difficult.
In this paper, the synthesis of 5-epi-Phomonol 1 and Phomonol 2 using commercially available triO-acetyl-D-glucal, as starting material, through the allyl alcohol 4.
OH
O
O
OH
t-Bu
O
Si
O
OH
OAc
t-Bu
O
OAc
t-Bu
O
O
5
1
Si
O
OAc
O
O
3
4
t-Bu
OH
O
Si
O
H
OH
t-Bu
O
O
t-Bu
O
O
6
2
Figure 1: Pathway of the obtention of the oxacycles Phomonol (2) and epi-Phomonol (1)
For the synthesis of 1, the side chain was the introduced in the position 5 using a Michael addition on
ketone 5. Removal of the silyl protecting group and a series of classical reactions, afforded 5-epiPhomonol.
Claisen rearrangement of the allyl vinyl ether derived from allylic alcohol 4 led to aldehyde 6, which
after a Wittig reaction afforded side chain in position 5 with the suitable stereochemistry. Using the
series of reactions described above would lead to Phomonol (2)1-2 (Figure 1).
Furthermore, in our group we developed a synthetic methodology for the preparation of oxacycles,
based in the oxidation of alkylfurans with singlet oxygen, followed by a hetero-Michael reaction.
Using this method we designed a synthetic approach towards Zoapatanol3.
References
(1)
(2)
(3)
Palakodety, R.K.; Sunchu P. Tetrahedron Lett., 2013, 54, 3788.
Basi, V.; Subba, R.; Lavudia S.; Pathuri, S. R.; Bhemavarapu, P. R.; Attaluri, R. P.; Jhillu, S.Y.; Helvetica
Chimica Acta; 2014, 9, 1326.
Canoa, P.; Gándara, Z.; Pérez, M.; Gago, R.; Gómez, G.; Fall, Y. Synthesis 2011, 431.
CF18. Characterization and quantification of copper nanoparticles
using single particle inductively coupled plasma-mass spectrometry
(SP-ICP-MS)
Beatriz Esperón-Baúlo, Elena Peña-Vázquez, Mª Raquel Domínguez-González, Mª Carmen
Barciela-Alonso, Pilar Bermejo-Barrera
University of Santiago de Compostela, Department of Analytical Chemistry, Nutrition and
Bromatology, Faculty of Chemistry, Av. das Ciencias, s/n 15782, Santiago de Compostela, Spain
[email protected]
The use of nanoparticles has increased in recent years. The nanoparticles that are more frequently
used in consumer products are metal oxide nanoparticles like TiO2, CuO, and ZnO. Environmental
and safety issues are important for copper nanoparticles due to their uses in marine paints, agriculture
biocides and wood preservatives.1 Recently, it has been reported their high cytotoxicity and ability to
cause DNA damage2, inhibit the growth and development of cotton plants3, and induce apoptosis in
the intestine of juvenile fishes (Epinephelus coioides)4.
Single particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) is an emerging
analytical technique to determine particle number concentration, particle size and size distribution
simultaneously. This method is based on the extremely sensitive metal detection capability of ICPMS, but in contrast to traditional ICP analysis, thousands of individual intensity readings are acquired,
each one with a very short dwell time.5 When one particle is introduced into the ICP, the atoms of the
analyte produce a flash of gaseous ions in the plasma, which are measured as a single pulse by the
detector. So, if one nanoparticle is introduced into the ICP during the reading time, the number of
counts of the pulse is related to the quantity of analyte atoms in the particle, and the frecuency of the
pulses is proportional to the number concentration of nanoparticles.6
The objective of this study is the development of an analytical method for the detection and
characterization of copper nanoparticles. The instrumental operating conditions were selected
(optimization of nebulization gas flow, torch position, deflector voltage, selection of isotopes, dwell
time, readings, etc…). In optimal conditions, standards of ionic copper and a certified reference
material of gold nanoparticles were used for calibration, and to calculate the concentration and size
of the nanoparticles.
Experiments were performed to prepare suspensions of Cu and CuO nanoparticles using stabilizers
(ethylene glycol, glycerin, lactose), sonication in an ultrasonic bath, and different sonication times.
The analytical characteristics of the method (limits of detection in size and concentration,
reproducibility, recovery) were also evaluated.
References
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Navratilova, J.; Praetorius, A.; Gondikas, A.; Fabienke, W.; von der Kammer, F.; Hofmann, T. Int. J. Res. Public
Health 2015, 12, 15756-15768
Karlsson, H.; Cronholm, P.; Gustafsson, J.; Möller, L. Chem. Res. Toxicol. 2008, 21, 1726-1732
Le Van, N.; Ma, C.; Shang, J.; Rui, Y.; Liu, S. Chemosphere 2016, 144, 661-670
Wang, T.; Long, X.; Liu, Z.; Cheng, Y.; Yan, S. Fish Shellfish Immunol. 2015, 44, 674-682
Mitrano, D. M.; Lesher, E. K.; Bednar, A.; Monserud, J.; Higgins, C. P.; Ranville, J. F. Environ. Toxicol. Chem.
2012, 31, 115-121
Laborda, F.; Jímenez-Lamana, J.; Bolea, E.; Castillo, J. R. J. Anal. At. Spectrom. 2011, 26, 1362-1371
Laborda, F.; Jímenez-Lamana, J.; Bolea, E.; Castillo, J. R. J. Anal. At. Spectrom. 2013, 28, 1220-1232
CF19. Palladium and ruthenium compounds derived from
polydentate ligands
Patricia Gaudino
Facultade de Ciencias, Universidade da Coruña, E-15071, A Coruña, Spain
[email protected]
This end of master project is dedicated to the synthesis and structural characterization of ruthenium
and palladium complexes derived from hydrazone ligands.
These ligands have been prepared easily by condensation of salicylaldehyde or 2-acetylpyridine and
1-methyl-1-phenylhydrazine and potentially are able to behave as tridentate ligands [C,N,O] and [C,
N, N], respectively1.
The reaction of the potentially [C,N,O] hydrazone with palladium(II) acetate in toluene yielded a
cyclometallated complex with tetranuclear structure in which the phenolate oxygen atoms are
bridging two monomeric moieties.
However, the reaction of the [C, N, N] hydrazone with palladium acetate, under similar conditions,
yielded a mononuclear complex in which the ligand acts as tridentate and an acetate ligand is also
coordinated to the metal centre. The reaction with lithium tetrachloropalladate gave a similar complex
with the hydrazone acting as a [C,N,N] ligand, and the acetate has been replaced by a chloride ligand.
These compounds belong to the category of cyclometallated organometallic compounds,
characterized by the formation of a chelate ring containing a Pd-C bond.
However, the reaction of the potentially [C,N,O] ligand with [RuCl(μ-Cl)(p-cymene)]2 gave a
complex in which the ligand is not cyclometallated, acting as bidentate [N, O]2 (2); the coordination
sphere around the ruthenium atom is completed with the p-cymene ligand, which behaves as
hexahapto, and a chloride ligand.
All the compounds were characterized using appropriate techniques: IR, NMR 1H and 13C-{1H}, mass
spectrometry and conductivity measurements.
OH
H
Me
N
N
+ [Ru(pcimeno)Cl2 ]2 + NaOAc
CH 2 Cl2
H
Me
O
Ru
N
Cl
N
References
(1)
(2)
Alberto Fernández, Digna Vázquez-García, Jesús J. Fernández, Margarita López-Torres, Antonio Suárez, José
M. Vila, Journal of Organometallic Chemistry 658 (2002) 15 20
Mark R. Crimmin, Denise A. Colby, Jonathan A. Ellman and Robert G. Bergman Dalton Trans., 2011, 40, 514
CF20. Bisthiosemicarbazone and thiocarbohydrazide ligands as
precursors of helical and meso-helical architectures
Sandra Fernández Fariña
Centro Singular de Investigación en Química Biológica y Materiales Moleculares (CIQUS),
Campus Vida, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, España
[email protected]
Metallosupramolecular compounds have attracted a great deal of attention over the past two decades
largely because of their unique, highly complex structural characteristics and their potential
electronic, magnetic, optical, and catalytic properties. These molecules can be prepared with relative
ease using coordination-driven self-assembly techniques.1 Among the wide variety of supramolecular
species reported to date, helicates and meso-helicates or mesocates are considered the simplest and
most fundamental architectures.2
Our research group has pioneered the use of bisbidentate thiosemicarbazone ligands that incorporate
a short spacer to achieve helical or meso-helical arrays. An overview of the previous results shows
that ligand design is a crucial tool for the formation of discrete or extended supramolecular
architectures with promising functionalities.3
Herein we report the synthesis of two different ligands: tetradentate bisthiosemicarbazone (H2L) and
hexadentate phosphino-thiocarbohydrazone (H2L1) ligands and their derived metallosupramolecular
complexes that were obtained using two different methodologies: electrochemical [Co(II), Zn(II),
Cd(II) with H2L] and chemical synthesis [Cu(I), Ag(I), Au(I) with H2L1]. Both approaches have been
successful for the obtaining of supramolecular architectures like helicates or meso-helicates (Figure
1). We have checked the effect of different factors like metal ion, method and counterion on the final
architecture of the metallosupramolecular compounds.
Figure 1. X-ray structures of the dinuclear helicate [Co2L2] (left) and the dinuclear mesocate [Ag2(HL1)2]+ (right).
References
(1)
(2)
(3)
Albrecht, M.; Fiege, M.; Osetska, O.; Coord. Chem. Rev., 2008, 252, 812-824.
Piguet, C.; Bernardinelli, G.; Hopfgartner, G.; Chem. Rev.,1997, 97, 2005-2062.
Martínez-Calvo, M.; Pedrido, R.; González-Noya, A. M.; Romero, M. J.; Cwiklinska, M.; Zaragoza, G.;
Bermejo, M. R.; Chem. Commun., 2011, 47, 9633-9635.
CF21. A new procedure for the preparation of ε-caprolactam and
synthesis of ionic liquids for different applications
Verónica Fernández Stefanuto
Department of Organic Chemistry, Faculty of Chemistry, University of Vigo, Vigo, Spain.
[email protected]
The Beckmann rearrangement, used to convert a ketoxime to the corresponding amide, is one of the
classical and most popular reactions in organic chemistry1. It is successfully applied in the industry
to produce ε-caprolactam (1,Figure 1), the basic monomer for manufacturing the synthetic fiber
Nylon 62.This reaction, however, requires high reaction temperature and strong acid media (usually,
generated with H2SO4), which causes serious corrosion problems and a large amount of by-products.
Thus, milder routes are required and alternative methods have been studied.
N
OH
O
NH
H 2SO 4
T
1
Nylon 6
Figure 1. Beckmann rearrangement of cyclohexanone oxime to produce ε-caprolactam
In a previous work3, we have performed the Beckmann rearrangement of several ketoximes by
treatment with tosyl chloride, using ionic liquids as both solvent and catalyst, without the need of
any other promoter. Now, a novel method to synthesize ε-caprolactam by using a guanidinium salt
as catalyzer is described.
Moreover, due to the wide range of possible combinations of cations and anions that can form an
ionic liquid, these are also called 'design solvents' because their structures can be designed adapting
them to the requirements of a particular application by varying its constituent ions.
In this work, its described the synthesis of several ionic liquids for various applications.
References
(1)
(2)
(3)
E. Beckmann, Chem. Ber. 1986, 89, 988-991
G. Dahlhoff, J.P.M. Niederer, W.F. Hoelderich, ε-Caprolactam: new by-product free synthesis routes, Cat. Rev.
2001, 43, 381-441
M. Vilas, E. Tojo, A mild and efficient way to prepare ε-caprolactam by using a novel saltt related with ionic
liquids, Tetrahedron Lett. 2010, 51, 4125-4128.
CF22. Metal-directed self-sorting of functionalized bipyridiniumbased ligands
Arturo Blanco; Tamara Rama, Marcos D. García; Carlos Peinador, José Mª Quintela
Facultade de Ciencias, Universidade da Coruña, E-15071 A Coruña, Spain
[email protected]
Within the field of supramolecular chemistry, the concept of self sorting can be defined as a selective
recognition phenomena in multicomponent heterogeneous mixtures that makes use of the diverse
types of non-covalent interactions (hydrogen bonds, metal-ligand interactions, solvophobic effects or
π-π stacking).1 This phenomena is common of the vast majority of biological processes, such as the
selective recognition of the heterocyclic bases within DNA.
In this context, the research shown herein has focused on the development of a three component
system, constructed by two N-monoalkyl-4,4’-bipyridinium-based ligands (1 and 2) and Pd(II)/Pt(II)
metal centers,2 able to exhibit a integrative social self-sorting behavior (Figure 1). Due to the presence
of donor (dioxonaphthalene) an acceptor (bypiridinium) aromatic units within the structure of the
functionalized ligand 1, its Pd(II)-directed self-assembly with the non-functionalized ligand 2 would
result into the inclusion complex I1 as the main species despite of the different potential outcomes of
the process (i.e. oligomeric species and three different metallocycles). This selective self-assembly
would result of the maximization of all the non-covalent forces involved in the process (metal-ligand,
p-p and hydrophobic interactions).
Figure 1: Intended self-sorted system
References
(1)
(2)
(a) Wu, A. X.; Isaacs, L. J. Am. Chem. Soc. 2003, 125, 4831-4835. (b) Safont-Sampere, M. M.; Fernández, G.;
Würthner, F. Chem. Rev. 2011, 111, 5784-5814.
(a) Rama, T.; Alvariño, C.; Domarco, O.; Platas-Iglesias, C.; Blanco, V.; García, M. D.; Peinador, C.; Quintela,
J. M. Inorg. Chem. 2016, 55, 2290-2298. (b) García, M. D.; Alvariño, C.; López-Vidal, E. M.; Rama, T.;
Peinador, C.; Quintela, J. M. Inorganica Chimica Acta. 2014, 417, 27-37.
CF23. Exploring the chemical and functional space of DNA-binding
metallopeptide cylinders
Jacobo Gómez González,a M. Eugenio Vázquez Sentís, b* Miguel Vázquez López a*
Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS) and
Departamento de Química Inorgánicaa and Química Orgánica,b Universidade de Santiago de
Compostela, 15782 Santiago de Compostela, Spain
[email protected]
Solid phase peptide synthesis methodology offers a great versatility to obtain different peptidic
chains. The use of artificial chelating amino acids derived from the ligand 2,2’-bipyridine (Bpy) allow
us to generate peptides which can coordinate metal ions, as Fe(II). These ions act as a template that
let the peptide chain to adopt a cylindrical shape that is the responsible of the DNA binding properties
of these metallosupramolecular compounds.1 The aim of my TFM is to use this methodology to
synthesize two new peptide ligands derived from the coordinating amino acid 1 able to coordinate
Fe(II) ions, thus generating the corresponding metallopeptide cylinders, and then to study the DNA
binding properties of these systems to different DNA secondary structures (DNA-duplex with
mitchmatches and 3WJ).
In the other hand, the metal ion used for constructing the metallopeptide cylinders depends on the
donor atoms that the artificial chelating residue owns. The Bpy binding unit of 1 is not suitable for
hard acids as Fe(III) or Ti(IV). In order to expand our synthetic approach to metal ions with large Q/r
ratio, we are trying to obtain a new artificial residue equipped with a catechol (Cat) chelating unit (2).
References
(1)
I. Gamba, G. Rama, E. Ortega-Carrasco, J.-D. Maréchal, J. Martínez-Costas, M. E. Vázquez, M. Vázquez
López, Chem. Commun. 2014, 50, 11097. 44 MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL
CF24. Detection of cations in aqueous medium by surface-enhanced
Raman scattering spectroscopy
Alberto Conde Valiño
Departamento de Química Física, Facultade de Química, Universidade de Vigo
[email protected]
Noble metal nanoparticles, such as Au, Ag or Cu, exhibit a characteristic property known as surface
plasmon resonance which is related to the collective oscillations of the conduction band electrons
when they are illuminated with light of appropriate wavelength. Consequently the electric field of
light is concentrated around the particle, amplifying the signal1. This property is responsible of the
multiple applications in different fields, among which includes sensing, based on surface plasmon
resonance (colorimetric sensing) or Surface-Enhanced Raman Scattering (SERS) spectroscopy.
SERS is a surface-sensitive technique based on the enhancement of Raman scattering (the inelastic
part of the light scattered by a molecule when illuminated)2 of molecules when they are located at the
plasmonic metal surfaces. This technique is a sensitive, versatile, and powerful analytical technique
with applications in chemistry, biochemistry, medicine, or environmental sciences, and with
sensitivity levels as low as a single molecule.
The aim of this paper is to develop a fast and simple methodology based a plasmonic nanostructured
platform to analyze the presence of cations in aqueous medium, particularly lead cations, by SERS.
This platform is based on gold nanoparticles (AuNPs) functionalized with glutathione (GSH). As
shown in scheme 1 the presence of Pb2+ leads to the selective aggregation of AuNPs and the
generation of hot-spots3. As a consequence it gives rise to the enhancement of the Raman signals
corresponding to GSH. Therefore detecting the glutathione we are able to detect Pb2+. Performing a
calibration curve we will try to correlate the SERS intensity with the lead concentration, allowing
identify different lead concentrations. Besides we will analyze the effect of NPs size in the detection
limit since the SERS efficiency is strongly dependent on the NPs dimensions. We will also analyze
the selectivity of this platform for lead, performing the study with other cations.
Scheme 1: Analysis of lead ions in water by SERS. 1) Functionalization of Au nanoparticles with
glutathione. 2) Au NP aggregation induced by Pb2+ ions. 3) Detection of Pb2+ ions based on SERS.
References
(1)
(2)
(3)
Kelly, K.L. Coronado, E. Zhao, L.L. Schatz, G.C. Journal of Physical Chemistry B 2003, 107(3): 668-677.
C. V. Raman; Krishnan, K. S., Nature 1928, 121, 501-502.
Xiang Mao, Zheng-Ping Li, Zhi-Yong Tang, Front Mater. Sci. 2011, 5(3): 322-328.
CF25. Extraction and determination of selenium and its species in
Brazil nuts (edible nut)
Adriana Mañana López, Jorge Moreda Piñeiro, Elia Alonso Rodríguez, Isabel Turnes Carou
Grupo Química Analítica Aplicada (QANAP), University Institute of Research in Environmental
Studies (IUMA), Centro de Investigaciones Científicas Avanzadas (CICA), Department of
Analytical Chemistry, Faculty of Sciences, University of A Coruña, Campus de A Coruña, s/n,
15071 A Coruña, Spain
[email protected]; [email protected]; [email protected]; [email protected]
The importance of selenium in human health and nutrition has long been recognized. In terms of
selenium speciation, its importance is based on the fact that this element is an essential component
due to acting in the cellular defense mechanism against oxidative damage by inhibiting toxic effects
of other heavy metals [1]. Brazil nuts have high naturally occurring selenium levels, since
concentrations of 600 µg g-1 have already been reported. Daily ingestion of only one nut can be
enough to make up the needs of an adult (55 µg day-1) [2]. The Brazil nuts showed only the organic
species selenomethionine and selenocystine, but only selenomethionine was found bioaccessible,
corresponding to 75-96% of the total selenium. In this work the feasibility of enzymatic hydrolysis
combined with pressurized liquid extraction (HE-PLE) for simultaneous extraction of selenium,
selenium species and other metals (As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na,
Ni, P, Pb, Rb, Sb, Si, Sn, Sr, Th, Ti, V, W y Zn) in Brazil nut was studied. Metal concentrations in
each experiment were assessed in de-fated Brazil nuts and compared with metal concentrations
achieved after Brazil nut microwave acid extraction (MAE) [3]. The extracted elements are
simultaneously determined by inductively coupled plasma-mass spectrometry (ICP–MS). Selenium
species were also quantified by ICP-MS after ionic exchange chromatography separation. Both
external calibration and standard addition calibration are used. Sc, Ge, Y, Rh and In are selected as
internal standards. The statistical significance of the variables involves on the extraction procedure
by HE-PLE (temperature, static time, pressure, protease mass, pH, TRIS concentration, DTT mass
(enzymatic activator)) was simultaneously evaluated by applying a Plackett–Burman experimental
design (2^8*3/64) approach [4]. The response variable was the mean percentage of released elements.
Mean percentage was calculated after metal concentration measured in each experience from
Plackett-Burman design and after achievement of recovery percentages (metal concentrations in
MAE extracts are considered as “certified values”). The design is analyzed by the main effect Pareto
chart. The results showed that TRIS concentration, extraction time, protease mass and temperature
are statistically significant variables (at 95% confidence level) for several metals (Ba, Co, Cu, Fe, K,
Mg, Mn, Ni, P, Rb, Se and selenium species) extraction by HE-PLE. The other metals was discarded
because concentration was below detection limit of method.
References
(1)
(2)
(3)
(4)
Yañez Barrientos, E.; Wrobel, K.; Torres Guzman, J. C.; Corrales Escobosa, A. R.; J. Anal. At. Spectrom; 2016,
31(1), 203-211.
Gomes da Silva, E.; Verola Mataveli, L. R.; Zezzi Arruda, M. A.; Talanta, 2013, 110, 53-57.
Kannamkumarath, S.; Wrobel, K.; Wuilloud, R.; Talanta, 2005, 66, 153-159.
Seppänen, M.; Kontturi, J.; López, I.; Madrid, Y.; Plant Soil, 2010, 337, 273-283.
CF26. Detection and quantification of toxins involved in Ciguatera
Fish Poisoning (CFP) in UE by LC/MS and comparison with the
mouse neuroblastoma assay
David Miguel Castro Alonso
Department of food and analytical chemistry, Facultad de Química, Universidad de Vigo (Vigo)
[email protected]
CFP is a human illnesses associated with the appearance of gastrointestinal and neurological
symptoms after consumption of fish contaminated by ciguatoxins (CTX´s), which precursors are
produced by benthic dinoflagellates in the genus Gambierdiscus. CTX´s-producing species are
endemic of coral reefs within the Caribbean sea, Indian and Pacific oceanic regions1. However, have
been recently confirmed cases of CFP in Canary Islands and other European regions and have been
identified tropical genus Gambierdiscus in the north Atlantic Ocean as well. This represents an
emerging public health problem in Europe.
CTX´s are structurally complex compounds and difficult to quantify, which is hard to set an acute
reference dose (ARD), although has been estimated more that concentrations at 0,1 ppb in flesh fish
causes CFP.
Recently episodes of CFP in EU forces to set and to develop an analytic method to be employed as a
routine method that will allow to confirm the presence of CTX´s in a sample and also to evaluate the
toxicological impact2.
This TFM propose two analytical methods, one based on HPLC-MS/MS for CTX´s detection and
quantification in contaminated fishes and the other one based on cytotoxicity assays like screening
method, which are able enough to detect CTX´s and also that ones allows the toxicological evaluation.
The initial results have shown that both methods have an adequate correlation, which allows confirm
the presence of CTX´s in the samples. However, the lack of standards and reference materials for
CTX´s are the main impediment to develop and to validate this methods.
Analysis of these toxins is complicated in complex biological matrix and in a very low concentration
due to the nature of the interferences into the matrixes which compete in the soft ionization sources.
Because of that, methods of extraction and purification are required in order to the correct
pretratament of the samples. In this line, in that academic practices it has been tried different methods
of sample extraction in order to improve the effectiveness of both methods proposed, which was a
great complement for the TFM.
References
(1)
(2)
(3)
Xu Y, Richlen ML, Liefer JD, Robertson A, Kulis D, Smith TB, et al. (2016). Influence of environmental variables
on Gambierdiscus spp (Dinophyceae) growth and distribution. Plos one 11(4): e0153197. Doi:
10.1371/journal.pone.0153197.
EFSA Panel on Contaminants in the Food Chain: Scientific opinion on marine biotoxinas in shellfish emerging
toxins: Ciguatoxin group EFSA Journal 2010; 8(6): 1627. (38pp). Doi: 10.2903/j.efsa.2010.1627.
Update on methodologies available for ciguatoxina determination: Perspectives to confront the onset of
ciguatera fish poisoning in Europe. Caillud A., De la Iglesia P., Darius H. T., Pauillac S., Aligizaki K., Fraga
S., Chinain M., Diogene J. (2010) Marine Drugs 8 (6), pp. 1838-1907
CF27. Post-run screening of lipophilic chlorinated pollutants in sludge
from urban sewage treatment plants
Mario Roca, Gabriela Castro, Isaac Rodriguez, María Ramil
Instituto de Investigación e Análises Alimentarias, Departamento de Química Analítica e
Bromatoloxía, Facultade de Química, Universidade de Santiago de Compostela
[email protected]
The feasibility of a post-run, automated search strategy for the detection and identification of
chlorinated compounds in the extracts of sludge samples, obtained from sewage treatment plants, is
presented. Comprehensive search of molecular entities in the LC-ESI(+)-QTOF-MS accurate, scan
records for extracts from sludge was carried out using dedicated software tools. Thereafter, empirical
formulae for compounds containing at least one atom of chlorine in their structure were generated.
Extracts were obtained from a pool of freeze-dried sludge samples by matrix solid-phase dispersion
(MSPD) with on-line fractionation of basic from acidic and neutral compounds. Both extracts were
then analysed by LC-QTOF-MS using a non-polar C18 column. Empirical formulae for molecular
entities identified in the recorded chromatograms (above 300 entities were found per chromatogram),
were proposed taking into account mass accuracy and isotopic profile. The mass defect between 35Cl
and 37Cl isotopes (meter data), combined with the typical profile of chlorinated compounds and their
anthropogenic origin were used to select those entities corresponding to chlorinated pollutants. After
molecular formula generation, product ion scan spectra were obtained considering different collision
energies. Analysis of product ion scan spectra, comparison with high resolution MS databases, insilico prediction of MS/MS fragmentation patterns and final comparison against standards of
candidate compounds were used for final identification of chlorinated compounds.
Following the above strategy, without retention time information, several chlorinated compounds,
recognized as ubiquitous in sludge samples, could be identified. Moreover, other species have been
detected and identified, for the first time, in this environment compartment. The list of novel detected
compounds comprises personal care products, pharmaceuticals and pesticides.
CF28. Pendant position effects on polyphenylacetilenes
Juan Luis Oubiña Allo
Department of Organic Chemistry,Singular Center of investigation in Biological Chemistry and
Molecular Materials, Faculty of Chemistry, University of Santiago de Compostela, Santiago;
[email protected]
Poly(phenylacetylene)s (PPA)s, are a family of helical polymers that belong to the “dynamic helical
polymers” in which, the helical sense and the helical scaffold can be tuned by external stimulis or
pendant groups with different structures.1
Because of these properties, polyphenylacetylenes bearing the (R)-α-hidroxy-α-phenylacetamide and
(S)-α-Chloro-α-phenylacetamide of 4-, 3-, and 2- ethynylaniline were prepared in order to determine
the effect of the para-, meta-, and ortho- substitution on the helical structure and the behavior of these
polymers in solution, due to the release of the steric hidrance when the pendat group is shifted from
para- toward ortho- position.
Elongation Effects
Compressed or Stretched Helix
R
R
H
H
n
H
n
n
R
p-PPA
m-PPA
R:
H
N
O
Ó
OH
o-PPA
H
N
O
Cl
References
(1)
E. Yashima, K. Maeda, K. Iida, K. Nagai, Chem. Rev. 2009, 109, 6102-6211.
CF29. Synthesis and reactivity of stannyl and germyl complexes of
ruthenium
Nuria Álvarez Pazos
Departamento de Química Inorgánica, Facultade de Química, Universidade de Vigo, Vigo
[email protected]
Ruthenium germyl and stannyl derivatives, [Ru]-GeR3 and [Ru]-SnR3, draw attention of several
research groups in recent years due to the great variety of reactions they can undergo, among which
nucleophilic reactions on germyl and stannyl groups can be highlighted.
Half-sandwich trichlorogermyl1, [Ru(GeCl3)(η5-Cp')L], and trichlorostannyl2, [Ru(SnCl3)(η5-Cp')L],
(Cp' = indenyl; pentamethylcyclopentadienyl, L= Ph2POCH(Ph)CH(Ph)OPPh2) complexes were
prepared by allowing chloro compounds [RuCl(η5-C5Me5)L] and [RuCl(η5-C9H7)L] to react with an
excess of GeCl2·dioxane and SnCl2·2H2O in ethanol, respectively. The treatment of these complexes
with different nucleophilic reagents like MgMeBr, LiC≡CPh or NaBH4 yielded the corresponding
compounds obtained by replacement of the three chlorides bonded to germanium and tin with the
nucleophile.
Cp'
Ph3 P
Ph3 P
PP
Ru
Cl
Cp'
Cp'
ECl2
P Ru
Cl
P
P
P
Ru
NuECl3
Cp'
P Ru
ENu3
P
P P=Ph 2POCH(Ph)CH(Ph)OPPh 2
E=Ge, Sn
Nu- = H -; PhC C -; MeThe complexes were characterized by spectroscopic techniques (IR and 1H, 31P{1H}, 13C{1H} and
119
Sn{1H} NMR) and the crystal structures of [RuCl(η5-C5Me5)L] and [Ru(GeCl3)(η5-C5Me5)L] were
resolved.
References
(1)
(2)
Albertin, G.; Antoniutti, S.; Castro, J.; Scapinello, F. J. Organomet. Chem. 2014, 751, 412-419.
Albertin, G.; Antoniutti, S.; Castro, J.; Da Lio, S. J. Organomet. Chem. 2013, 32, 3651-2661.
CF30. Bioorthogonal Chemistry of Copper (I) inside living cells
Joan Miguel Ávila, María Tomás-Gamasa, José Luis Mascareñas Cid*
Dpto. de Química Orgánica, Centro de Investigaciones en Química Biológica y Materiales
Moleculares (CIQUS), Universidad de Santiago de Compostela, 15782, Spain
[email protected]
Bioorthogonal chemistry has revolutionized the fields of imaging, drug development and
biotechnology, due to the ability to manipulate biomolecules inside living systems without disturbing
the host metabolism by means of functional groups inert or absent in nature.
The Copper Azide Alkyne Cycloaddition (CuAAC) is one of the most widely reactions used in
bioorthogonal chemistry due to its features as click reaction: high yields, minimal byproducts, mild
conditions aso. Nevertheless, “not all that glitters is Copper” as it exhibits a pronounced cytotoxicity,
due to its capacity to generate reactive oxygen species (ROS) and its pronounced thiophilic character.
The discovery of tris(triazolylmethyl)amine ligands, such as TBTA or BTTE, that protect copper
from oxidation, has allowed the development of non-natural reactions on cell surface or even inside
E. Coli.1
Herein we report the synthesis of BTTE analogues coupled with different phosphonium derivatives.
This new kind of molecules not only preserve the strengths of the BTTE ligands, but also act as
mitochondrial targeting vectors, promoting the localization and accumulation of the catalyst inside
this organelle in HeLa cells. Moreover, the new catalyst has been equipped with a fluorescent moiety
for its visualization.
The new complexes have been used as catalysts in the intermolecular reaction between an azide and
different alkynes, which leads to fluorescent triazoles. In vitro experiments have been carried out and
we are currently translating this chemistry to HeLa cells. Furthermore, to the best of our knowledge,
this is the first example of an intermolecular copper catalyzed azide-alkyne coupling inside living
cells.
References
(1)
(2)
Yang, M.; Jalloh, A. S.; Wei, W.; Zhao, J.; Wu, P.; Cheng, P. R.; Nat Comm. 2014, 5, 4981.
Smith, R. A. J.; Hartley, R. C.; Cochemé, H. M.; Murphy, M. P.; Trends Pharmacol Sci. 2012, 33, 341.
CF31. Synthesis and Characterization of Macrocyclic Ligands and
their Metallic Complexes
Laura Caneda-Martínez
Departamento de Química Fundamental, Facultad de Ciencias, Universidade da Coruña, A
Coruña
[email protected]
In this work, the 18-membered hexaazamacrocyclic ligand L (Figure 1) has been synthesized by
asymmetric alkylation of the parent ligand L1 with the assistance of protecting groups. The large
cavity of the macrocycle, as well as the increased denticity achieved by means of the addition of the
three coordinating pendant arms, provides the ligand with the ability to coordinate effectively with
large metal ions. Given their relevance to Molecular Imaging techniques, the ions selected to form
complexes with the macrocycle L have been Gd(III) and Y(III).
O
N
NH
NH
OH
N
HN
N
HN
N
N
N
N
N
HO
O
L1
O
OH
L
Figure 2
According to previous reports,1,2 Gd(III) complexes have the tendency to adopt 10-coordinated
geometries in systems with similar characteristics to the ligand under study. Thus, the macrocycle L
- which possesses nine potential coordinating positions - might not satisfy the coordination
requirements of this cation, therefore allowing the introduction of a water molecule from the solvent
into the coordination sphere. Should this be the case, the Gd(III) complexes prepared with ligand L
could be presented as promising contrast agent candidates for Magnetic Resonance Imaging.
Moreover, it must be noted that the alkylation with the benzyl group can be selectively reversed
through hydrogenation. As a result, once the secondary amine is recovered, it can be functionalized
a second time with a linker capable of allowing bioconjugation with a relevant macromolecule.
Consequently, ligand L is expected to be a competent precursor of bifunctional chelators for 86Y
radiopharmaceuticals for Positron Emission Tomography.
References
(1)
(2)
Valencia, L.; Martínez, J.; Macías, A.; Bastida, R.; Carvalho, R. A.; Geraldes, C. F. G. C. Inorg. Chem. 2002,
41, 5300-5312
Miao, L.; Bell, D.; Rothremel, G.; Bryant, L. H.; Fitzsimmons, P. M.; Jackels, S. Supramol. Chem. 1996, 6, 365373.
CF32. Rhenium(I) complexes as 99mTc surrogates for estrogen
receptor imaging
Saray Argibay Otero
Departamento de Química Inorgánica, QI5, Universidade de Vigo
[email protected]
99m
Tc compounds with selective affinity for estrogen receptor (ER) can be used in tumor and
hormone-dependent diseases diagnosis (for example breast cancer)1. Nevertheless rhenium
surrogates are often used in the first steps in technetium radiopharmaceuticals design because of the
difficulty of working with radioactive metals and taking advantage of similar chemistry of both
metals.
In our group, several rhenium thiosemicarbazonate complexes with potential affinity for the ER have
been designed, synthesized and characterized2. The affinity tests performed at USEF/USC suggested
very promising results, after introduction of additional groups for optimizing interaction site specific
receptor.
The new designed complexes try to simulate the raloxifene interaction (an agonist with high affinity
by the receptor) with the binding site of ER (Figure 1, left). These rhenium(I) complexes have a
octahedral surrounded formed by three carbonyl groups in fac, one thiosemicarbazone bidentate
ligand and one pyridine p-derivative monodentate ligand (Figure 2, right). R chains which contain
hydroxyl and tertiary amino groups will interact by hydrogen bond and electrostatic forces with
amino acids His, Arg, Glu and Asp of the binding site.
Figure 1
Ligands and complexes has been characterized by NMR, IR, elemental analysis and mass
spectroscopy. Some of these compounds were also studied by X ray diffraction. Studies of the crystals
structures and determination of the role of hydrogen bond interactions with other molecules suggest
a good affinity by ER.
References
(1)
(2)
Biological Inorganic Chemistry : Structure and Reactivity; Bertini, I.; Gray, H.; Stiefel, E.; Valentine, J.;
University Science Books, 2007. Chapter VII.
Núñez-Montenegro, A.; Carballo, R.; Vázquez-López E.; J. Inorg. Biochem. 2014, 140, 53-63.
CF33. Synthesis of Dendrimers by Azide-Alkyne Cycloaddition
Ágata Millán García
Department of Organic Chemistry,Singular Center of investigation in Biological Chemistry and
Molecular Materials, Faculty of Chemistry, University of Santiago de Compostela, Santiago
[email protected]
Dendrimers are synthetic branched macromolecules composed of repetitive layers of branching unit
s that emerge from a central core.The synthesis of dendrimers is a slow process that requires extensi
ve purification steps. However, the "Click Chemistry" was presented as a powerful tool in the constr
uction of dendritic fragments. Thanks to these processes exhibit high reactivity and orthogonality, th
is kind of branched structures can be obtained in high yield and requiring only simple purifications.
An example of this chemistry is the azide-alkyne cycloaddition (AAC) (Scheme 1), which in its clas
sical thermal version leads the formation of not regioselective 1,2,3-triazoles.
Scheme 1: Schematic representation of the thermal cycloaddition [3+2] azide -alkyne
However, in 2002, groups Meldal and Sharpless and Fokin discovered that the addition of catalytic a
mounts of a copper salt produced a significant increase in the reaction rate, which allows performing
these transformations at room temperature in very short reaction regioselectively yielding 1,4- disub
stituted triazoles (Scheme 2). However, azide -alkyne cycloaddition the catalyzed by Cu (I), (CuAA
C) , the presence of copper has limited the use of this reaction for applications in living systems and
biomedical applications due to their cytotoxic effects.
Scheme 2: Schematic representation of the cooper catalized thermal cycloaddition [3+2] azide-alkyne
Therefore , the synthetic strategies combining practical use and advantages of the CuAAC without t
he need for a metal catalyst , would be of great value in biological applications. Consequently , in re
cent years they have been studying alternatives to using metal catalysts. This "Metal - free Click Ch
emistry" is a growing field of research and developing.
CF34. Synthesis and Characterization of Ammonium Salts based on
Cromoglicic Acid
Fernán Berride García
Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, Vigo.
[email protected]
Cromoglicic acid (1), also called Cromolyn, is a drug that prevents the release of inflammatory
chemicals such as histamine, stabilizing mast cells. This permits its use in allergic rhinitis, asthma or
mastocytosis. Also, in its disodium salt form, shows a lyotropic liquid crystal behavior1.
In a thesis made in this department2, some ammonium salts based in cromolyn were synthesized. In
this work a new batch of ammonium salts derived of Cromoglicic Acid and tetrabutylammonium or
TBA (2), choline (3), hexylamine (4) and decylamine (5), was prepared by mixing the acid and the
corresponding amine/hydroxyammonium salt in Dimethylsulfoxide (DMSO) or Acetonitrile in good
yields.
The characterization was made by means of both 1H, 13C NMR and Infrared Spectroscopy, combined
with Elemental Analysis for all the ammonium salts made.
After that, solubility of each ammonium salt was studied in different solvents. They showed good
solubility in water, methanol and DMSO, while in acetonitrile and chloroform solubility decreases.
In the case of non-polar solvents, such as toluene, ammonium salts showed slightly to no solubility.
Finally, gelation of such solvents by the aforementioned ammonium salts will be studied, varying the
concentration of the ammonium salt used.
References
(1)
(2)
Lydon, J. Liq. Cryst. 2011, 38 (38), 11–12.
Troche, E. NMR in Oriented Media. New Methodologies and Studies on New Alignment media, University Of
Vigo, 2015.
55 MÁSTER UNIVERSITARIO EN INVESTIGACIÓN QUÍMICA Y QUÍMICA INDUSTRIAL Curso académico 2015‐2016 MAPA DE SITUACIÓN Entradas Campus Entrada CICA Facultad de Economía y Empresa
56 Minisimposio Interuniversitario Máster en Investigación Química y Química Industrial FINANCIADO XII Ciclo de conferencias “Perspectivas da Investigación Química Actual” de la UDC Agrupación Estratégica CICA‐INIBIC, (AGRUP2015/05) 57

curso académico 2015‐2016 - USC-UDC-UVI

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