CQB

The Centro de Química e Bioquímica was founded in 2001 aiming at developinginternationally competitive science, particularly at the frontier of chemistry andbiochemistry. The multidisciplinary teams working in the experimental andtheoretical labs within CQB involve approximately sixty PhD members and morethan one hundred collaborators, most of them PhD and Master students. Thelively and youthful atmosphere of the Faculdade de Ciências extends to CQBand is further amplified by the large number of international collaborations andprograms (students from ERASMUS, IAESTE and others).

We conduct fundamental research disseminated by recognized peer-reviewedscientific journals, and the high number of citations reflects its relevance to thescientific community worldwide.

CQB research is organized in two thematic lines, which are aligned with theSocietal Challenges defined in Horizon 2020 EU, the priorities for the regionaldevelopment of the Lisbon area, and take advantage of the consolidated skillsof CQB members:

Chemistry and Biochemistry for a Clean Environment

Healthy Life: Molecular Interventions and Regulation Mechanisms

I invite you to read these pages, visit our website and know more about us andour research!

Lisbon, November 15, 2015

Maria José Calhorda(CQB coordinator)

Photo: CQB day – September 2015

Index

Mission 1

We are 2

Indicators 4

Achievements 5

Participation in National & International Organizations 11

Networking 13

Smart Specialization 16

Knowledge Transfer 17

Outreach activities 18

The Thematic Lines 21

Chemistry and Biochemistry for a Clean Environment 23

Healthy Life: Molecular Interventions and Regulation Mechanisms 27

Groups & Highlights 31

CQB Publications 79

Equipment 85

CQB has….

Excellence in scientific production

Research goals aligned with EITHealth, H2020 and the StrategicPriorities for the Region of Lisbon, namely those concerning theSmart Specialization

Networking in EIP AHA, EITHealth – INNOStar, COST programs, SoftMatter@PT Network, Health Cluster Portugal, Colleges “Brain” and“3F (Farm, Food, Forestry)” at ULisboa.

A collaborative culture, as attested by joint programs with industryand academia at the national and international level

Privileged interactions with society

Mission

The mission of CQB is grounded on three pillars: toinvestigate challenging problems in chemistry andbiochemistry, to train the next generation of highly skilledchemists and biochemists, and to create social, economic andcultural value from scientific knowledge.

1

We are

61 Integrated Members (IM)

& 115 Students

IMStudents0

10

20

30

40

50

60

University Staff56%

Post Doc29%

FCT Investigators 15%

2

We are

Groups network12 Research Groups

AAM Adsorption and Adsorbent MaterialsCC Carbohydrate Chemistry EMBS Environmental and Biological Mass SpectrometryE EnzymologyITC Inorganic and Theoretical Chemistry IE Interfacial ElectrochemistryMB Molecular BiophysicsME Molecular EnergeticsRB Redox BiologySST Separation Science and TechnologySSC Solid State ChemistrySR Structure and Reactivity

3

CQB Indicators

0

20

40

60

80

100

120

140

160

1 2 3 4 5

Ph.D. theses MSc. theses Publications

2010 2011 2012 2013 2014 Year

623 Publications 2008- 2012 ~104 / year

246 Publications 2013-2014 123 / year

• 27% with international collaborations• 18% with internal collaborations• 15% in Top 10% journals*• 65% in Top 25% journals* (Q1)

*by impact factor and subject area

Indicators 2008 2009 2010 2011 2012 2013 2014

Integrated Members 52 54 61 60 66 64 61

PhD theses 12 10 12 14 9 12 5

MSc theses 46 34 30 31 28 22 27

Papers in International peer reviewed journals

96 88 98 101 109 99 117

International Books/book chapters

5 2 7 1 14 6 1

Patents 1 6 2 5 7 3 1

In 2014, publications included

•Hundreds of oral & poster presentations in international conferences each year•Organization of national and

international conferences

In 2015 80 papers in International

peer reviewed journals

3 Book Chapters

4

Achievements - Investigador FCT

7 successful applications in the 2012, 2013 and 2014 calls

CQB receives a comparatively large number of applications which have ahigher degree of success than the national average rate in this highlycompetitive program.

Researchers and projects

2012 Call

Carla D. Nunes, Developing Grant: Innovative Concepts in AsymmetricCatalysis

Rodrigo F. M. de Almeida, Developing Grant: Tackling Membrane LipidOrganization to Understand and Refine Drug Mechanisms of Action

2013 Call

Ana S. Viana, Starting Grant: Novel Nanotructured Electrodes towardsOptimal Biosensing

Nuno M. Xavier, Starting Grant: Synthesis of Nucleotide Mimics asPotential Antitumor Agents Targeting Cyclin-dependent Kinases

2014 Call

Gonçalo Costa, Starting Grant: Revealing Amyloid Fibril Formationthrough the ions of Mass Spectrometry

Olinda Monteiro, Starting Grant: Titanate nanotubes photosensitizationby narrow bandgap semicondutor nanoparticles

Paulo Costa, Starting Grant: Halogen Bonds in (Bio)chemical Systems: aTheoretical Approach for ‘Real World’ Applications

FCT investigator program is a researcher-centered, highly competitivescheme, aimed at providing 5-year support for the most talented andcreative researchers, capable of carrying out independent research andbecoming leaders in their fields. info: www.fct.pt

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Achievements - Papers

Molecular details of INH-C10 binding to wt KatG and to its S315T mutante,V.H. Teixeira, C. Ventura, R. Leitão, C. Rafols, E. Bosch, F. Martins, M.Machuqueiro, Mol. Pharmaceutics, 2015, 12, 898−909.

Effect of the irradiation wavelength on the performance of nanoporouscarbon as an additive of TiO2, M. A. Andrade, A. S. Mestre, R. J. Carmona, A.P.Carvalho, C. O. Ania, Appl. Catal. A : General, 2015, 507, 91–98.

New long circulating magnetoliposomes as contrast agents for detection of ischemia-reperfusion injuries by MRI, M.B.F. Martins, M.L. Corvo, P. Marcelino, H.S. Marinho, G. Feio, A. Carvalho, A. Nanomed.-Nanotechnol. Biol. Med.,2014, 10, 207-214.

Crystallization around solid-like nanosized docks can explain the specificity,diversity and stability of membrane microdomains, R.F.M. de Almeida and E.Joly, Front. Plant Sci.,2014, 5, 72.

Exploiting the Therapeutic Potential of 8-ß-D-Glucopyranosylgenistein:Synthesis, Antidiabetic Activity and Molecular Interaction with IAPP and Aß1-42, A.R. Jesus, C. Dias, A.M. Matos, R.F.M. de Almeida, A.S. Viana, F. Marcelo, R.T:Ribeiro, M.P. Macedo, C. Airoldi, F. Nicotra, A. Martins, E.J. Cabrita, J. Jiménez-Barbero, A.P. Rauter, J. Med. Chem., 2014, 57, 9463-9472.

Differential Interactions of Rifabutin with Human and Bacterial Membranes:Implication for Its Therapeutic and Toxic Effects, M. Pinheiro, M. Arêde, J. M.Caio, C. Moiteiro, M. Lúcio, S. Reis, J. Med. Chem.,2013, 56, 417-426.

Kinetics and Mechanism of the Thermal Dehydration of a Robustand Yet Metastable Hemihydrate of 4-Hydroxynicotinic Acid, A.Joseph, C. E. S. Bernardes, A. S. Viana, M. F. M. Piedade, M. E. Minasda Piedade, Crystal Growth & Design 2015, 15, 3511-3524.

Helical Channel Mesoporous Materials with Embedded MagneticIron Nanoparticles: Chiral Recognition and Implications inAsymmetric Olefin Epoxidation, C.I. Fernandes, G. B. G. Stenning, J.D. Taylor, C. D. Nunes, P.D. Vaz, Adv. Synth. Catal., 2015, in press.

Highly enantioselective olefin epoxidation controlled by helical

confined environments, C. I. Fernandes, M. S. Saraiva, T. G. Nunes,P. D. Vaz, C. D. Nunes, J. Catal., 2014, 309, 21-32.

Top 5%

Top 10%

6

Achievements - PapersKey Scientific Articles classified by

Effect of luteolin and apigenin on rosmarinic acid bioavailability in Caco-2 cellmonolayers, P.L. Falé, L. Ascensão, M.L. Serralheiro, Food Funct. 2013, 4:426.

Cellular polarity in aging: role of redox regulation and nutrition, H. Soares, H.S.Marinho, C. Real, F. Antunes, Genes Nutr. 2014, 9: 371.

Mob1: defining cell polarity for proper cell division, A. Tavares, J. Gonçalves, C.

Florindo, A.A. Tavares, H. Soares, J. Cell Sci.,2012, 125, 516-527.[RuII(η⁵-C₅H₅)(bipy)(PPh₃)]⁺, a promising large spectrum antitumor agent: cytotoxicactivity and interaction with human serum albumin. Tomaz A.I., Jakusch T., Morais T.S., Marquês F., de Almeida R.F., Mendes F., EnyedyE.A., Santos I., Pessoa J.C., Kiss T., Garcia M.H.J. Inorg. Biochem. 2012,117:261.

Non-Coding RNAs: Multi-Tasking Molecules in the Cell., A.Q. Gomes, S. Nolasco, H.Soares, Int. J. Mol. Sci.2013, 14,16010-39.

GeL domains in the plasma membrane of Saccharomyces cerevisiae: highly ordered,ergosterol-free, sphingolipid-enriched lipid rafts, F. Aresta-Branco, A.M. Cordeiro,H.S. Marinho, L. Cyrne, L., F. Antunes, R.F.M. de Almeida, J. Biol. Chem.,2011, 286,5043-5054. – EXCEPTIONAL PAPER.

Scientific Articles recommended by

ISI highly cited paper - Top 1% in Pharmacology andToxicology

Marketed marine natural products in the pharmaceutical and cosmeceuticalindustries: tips for success, A. Martins, H. Vieira, H. Gaspar, S. Santos, Marine Drugs2014 12(2), 1066-1101 (Review paper).

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Achievements - Papers

2 scientific dissemination papers written by young CQBresearchers, 2013

These papers were chosen after a selection process with only 1%successful applications around Europe and were published in 2013:

The Permanent Platform for European Excellence – Atomium Culture(sponsored by the European Commission)

“El País” (Spanish newspaper) “Il sole 24 Ore” (Italian newspaper)

↘ Therapeutic properties of nitric oxide Moisés Luzia Pinto

↘ Rafts in our cells: a new role for lipids in the molecular organization of life

Rodrigo F. M. de Almeida

8

ISI highly cited paper - Top 1% in Biology and Biochemistry

Hydrogen peroxide sensing, signaling and regulation of transcription factors, H.S.Marinho, C. Real, L. Cyrne, H.Soares, F. Antunes, Redox Biol.,2014, 2014, 535.

Achievements - Prizes

Second Prize of the Crystals in Art CompetitionThe British Association for Crystal Growth 2014

Crystals of 4’-hydroxyacetophenone (polymorph I)by Carlos Bernardes

9

Food & Nutrition Awards 2014:L. Serralheiro and P. L. Falé, CQB won2nd Honorable Mention in thecategory of Research & Development

Infusions to reduce blood cholesterol and improve digestion

Project awarded under Programa de Estímulo à Investigação, Fundação Calouste Gulbenkian

To distinguish and stimulate research of highlypromising young researchers (under 26 years), to helpachieving the scientific goals of the project.

Sara Realista, CQB PhD student, won the prize in the area of Chemistry, withthe project: "Smart polymer switches for green CO2 capture“, March 2014.

Achievements - ImagesCover of ChemCatChem 2014, 6

Dinuclear Zinc–N-Heterocyclic CarbeneComplexes for Either the Controlled Ring-Opening Polymerization of Lactide or theControlled Degradation of Polylactide UnderMild Conditions, C. Fliedel, D. Vila-Viçosa, M.J. Calhorda, S. Dagorne, T. Avilés,ChemCatChem 2014, 6: 1357 – 1367.

Image displayed in 2015 at the Homepage of the

Sociedad de Biofísicos Latino Americanos (SOBLA)

10

In : de Almeida, R.F.M.* and Joly, E.*, 2014. Crystallization around

solid-like nanosized docks can explain the specificity, diversity and

stability of membrane microdomains. Front Plant Sci. 5;5:72.

Participation in National & International organizations

Participation in editorial boards of international scientific journals

Editor of the Royal Society of Chemistry Book Series Specialist Periodical Reports entitled Carbohydrate Chemistry – Chemical and Biological Approaches (A. P. Rauter)

Associate Editor of Mediterranean Journal of Chemistry (A. P. Rauter)

Associate Editor of Frontiers in Cell and Developmental Biology (F. Antunes)

Associate Editor of RSC Advances (P.D. Vaz)

Advisory Board of Journal of Chemical Thermodynamics (M.Minas da Piedade)

Advisory Board of European Journal of Organic Chemistry (A. P. Rauter)

Editorial Board of Journal of Carbohydrate Chemistry (A. P. Rauter)

Editorial Board of Drug Design Methodologies and Modern Medicinal Chemistry (A. P. Rauter)

Editorial Board of Frontiers in Membrane Physiology and Biophysics (R. F. M. de Almeida)

11

Participation in National & International Organizations

Participation in decision-making bodies and in International andNational Organizations, Committees and Divisions

• Sociedade Portuguesa de Química, President (M.J. Calhorda)

• IUPAC Division (VIII) of Chemical Nomenclature and Structure Representation, Titular member (A. P. Rauter)

• IUPAC Interdivisional Committee on Terminology, Nomenclature and Symbols (ICTNS) (Associate member) and Division VIII representative in ICTNS (A. P. Rauter)

• IUPAC Division (III) of Organic and Biomolecular Chemistry, Associate member and Secretary (A. P. Rauter)

• Chief Operational Officer of the LisbonLiving+ Consortium and member of its Executive Committee (2013-Sept.2014), established for the application to the EIT KIC on Healthy Life and Active Ageing EITHealth (A. P. Rauter)

• FCUL Sponsor of the FCT-PhD Program Catalysis and Sustainability (CATSUS) (M.J. Calhorda)

• Steering Committee of the Technology Transfer Unit of the University of Lisbon UL-INOVAR (2009-2013) (A. P. Rauter)

• International Society of Electrochemistry, National Representative (J.Correia)

• International Carbohydrate Organisation National Representative (A. P. Rauter)

• Rede Nacional de Espectrometria de Massa (M. H. Florêncio: Coordinator)

• Rede Procura: Associação Portuguesa de Proteómica (A. Ferreira, Member of AuditCommittee Board and C. Cordeiro, Secretary of the General Council)

• Conselho Geral da Universidade de Lisboa (H.Florêncio)

• Autoridade da Segurança Alimentar e Económica, ASAE (H.Florêncio)

12

CQB NetworkingThe European Innovation Partnership on Active and Healthy

Ageing (EIP AHA), Action Group A3

Prevention of functional decline and frailty More than 70 consortia and institutions CQB belongs to the FCUL consortium

CQB activities and deliverables:

Interactive website to educate the general public (functional foods for disease prevention)

e-learning courses chemical and biological approaches towards innovative molecular entities

and functional food ingredients understanding the mechanisms of frailty and ageing novel high-added products from biomass

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CQB NetworkingCMST COST Action CM1102 - Multivalent Glycosystems for Nanoscience –MultiGlycoNano (2011-2015), MC

CMST COST Action CM1205 - Catalytic Routines for Small Molecule Activation(CARISMA) (2013-2017), MC and WG2

CMST COST Action CM1301 - Chemistry for ELectron-Induced Nanofabrication(CELINA) (2013-2017), MC and WG2

CMST COST Action CM1302 - European Network on Smart Inorganic Polymers(SIPs), 2013-2017, MC and WG2

CMST COST Action CM1303 - Systems Biocatalysis (2013-2017), MC and WG5

CMST COST Action CM1305 - Explicit Control Over Spin-states in Technologyand Biochemistry (ECOSTBio) (2014-2018), MC

CMST COST Action CM1307 - Targeted chemotherapy towards diseases causedby endoparasites (2014-2018), WG

CMST COST Action CM1402 - From molecules to crystals - how do organicmolecules form crystals? (Crystallize) (2014-2018), MC and WG1, WG2, andWG4

FA COST Action FA1403 – Inter individual variation in response to consumptionof plant food bioactives and determinants involved (POSITIVe) (2014-2018),MC

BMBS COST Action BM1102 - Ciliates as model systems to study genomeevolution, mechanisms of non-Mendelian inheritance, and their roles inenvironmental adaptation (2011-2015),MC

CMST COST Action CM1406 - Epigenetic Chemical Biology (EPICHEM) (2015-2019), MC

TD COST Action TD1402 - Multifunctional Nanoparticles for MagneticHyperthermia and Indirect Radiation Therapy (RADIOMAG) (2014-2018), MC

BMBS COST Action BM1403 - Native Mass Spectrometry and Related Methodsfor Structural Biology (2014-2018), MC

MPNS COST Action MP1302 - NanoSpectroscopy (2013-2017), WG

TD COST Action TD1305- iPROMEDAI: Improved Protection of Medical DevicesAgainst Infection (2014-2018), WG MC- Management committee

WG- Working Group

14

CQB NetworkingEIT-KIC/IVE/0051/2013

The European Institute of Innovation and Technology (EIT) haslaunched an application to a Knowledge and Innovation Community(KIC) on Healthy Life and Active Ageing

↘ FCT approved the project EIT-KIC/IVE/0051/2013 to prepare the application

↘ CQB is one of the founders of the consortium LisbonLiving+ built withinthis project. This consortium involves Industry, Governmental bodiesand Academia partners.

7th Sino-Portugal Scientific and Technological Cooperation, 2013-2015

↘ The Construction of Novel Sensitive Biosensing Interfaces forTumor Marker and BOD Detection.

15

Smart Specialization

New materials to monitor/ remove/ degrade prioritypollutants in complex matrices (e.g. drinking water) withmuch higher efficiency and lower cost than currentprocedures.

Innovative procedures for the recovery of Pt-groupmetals from hydrometallurgical chloride leaches.

Correlations of traditional knowledge with scientificevidence for Portuguese flora, as a source of functionalfoods and nutraceuticals.

The energetic valorization of olive-mill wastewaters andof cork industry by-products.

Development and application of new active substanceswith phytopharmaceutical use.

The identification of bioactive compounds in marinefauna and flora resources.

Contracts and research projects with national and international Industries, collaboration with high-tech SMEs,

and governmental bodies, to develop:

Partnerships to assess biological activities towards causative bacterial agents ofglobal health threats.

Collaboration with PARALAB and NETZSCH on testing the Premium DifferentialScanning Calorimeter, DSC 204 F1 Phoenix

Contract between Laboratórios Atral S.A. and CQB for analytical services Collaboration with Autoridade de Segurança Alimentar e Económica

Collaboration with Laboratório de Polícia Científica da Polícia Judiciária

Identification of new psychoactive substances marketed as recreational drugsin Portugal.

16

CQB was involved in launching three start-up companies:

Knowledge Transfer

Bio-additives for marine antifouling paintsNew marine leads

Filtering media forimproving indoor air quality

CQB Patents 2013-2015

Two-Component Natural Polymeric Water-Based Glues obtained from Derivativesof Cork. WO 2015034383 A1, 2015.

Functionalisation process for the biocides immobilisation in polymeric matrixes,E. R. Silva, O. Ferreira, J. C.M. Bordado, Patent PT Nº 10809, 2015.

Colas Naturais de Base aquosa, de dois componentes, obtidas a partir deDerivados de cortiça (Water-based natural glues obtained from cork derivatives).PT107143, 2013.

Utilization of olive bagasse as acetylcholinesterase inhibitor for cholinergicdiseases. PT105914B, 2013.

Applications of antioxidant and antiproliferative natural products from alfarrobabiomass. PT105731B, 2013.

New C-glycosylpolyphenol antidiabetic agents, effect on glucose tolerance andinteraction with beta-amyloid. Therapeutic applications of the synthesizedagent(s) and of Genista tenera ethyl acetate extracts containing some of thoseagents. WO201313247OA2, 2013 (Pending Patent ).

Compostos derivados de açúcar inibidores de espécies de bacillus, processo deobtenção e respectivas utilizações. PT105475, 2011. (Pending Patent)

17

Outreach Activities↗ CQB organizes annual meetings open to the academia and society, such asthe CQB day and workshops, to stimulate joint research and enhance publicvisibility.

CQB day – September 2015

↗ Set-up of a website (in Portuguese, 2012) to provide the general public withscientific information about antioxidants http://antioxidantes.fc.ul.pt/

↗Involvement in “Ciência Viva”: Action European Researchers Night

↗Talks, demonstrations and quizzes on FCUL Open Days and Futurália

↗Radio/TV broadcasts to comment scientific discoveries

CQB-Day15 de Setembro

2015Edifício C6 - Piso 2 Sala 6. 2. 56

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Outreach Activities Porque é que o Space Shuttle não anda a gasolina?

Video presention on the frame of Saber Porquê, O Programa o Mundo naEscola, promoted by Ministério da Educação e Ciência(www.mundonaescola.pt)

Trabalho experimental em Química no Ensino Secundário- Novosprogramas, novos desafios a partir de 2015/16; Short training/updatingcourses for secondary school teachers

Olimpíadas da Química Júnior, organized by SPQ

A Tabela Periódica no Dia Mundial do Ambiente

Erasmus +

•Staff mobility for teaching and training activities,La Sapienza University, Rome, Italy, May 2015

• International Week, University of Foggia, Italy, June 2015

19

20

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Thematic LinesChemistry and Biochemistry for a Clean EnvironmentCoordination: Carla D. Nunes

(FCT Principal Investigator)

Healthy Life: Molecular Interventions & Regulation MechanismsCoordination: Rodrigo F. M. de Almeida(FCT Principal Investigator)

↘Aligned with H2020 Societal Challenges↘Aligned with Lisbon area regional priorities

MCM-41-Mo is an agent for rhodamine B degradation

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Chemistry and Biochemistry for a Clean Environment

Overview and goals

Chemistry and Biochemistry for a Clean Environment focuses onthe European societal challenges to develop methodologies thatensure a clean and healthy environment. To achieve this, newways of identifying, assessing, preventing, controlling, orefficiently removing contaminants, thereby reducing humanhealth risks, will be addressed. In parallel, we create selective andenvironment friendly catalyst for industrial relevant processes.

CQB has the expertise to synthesize and characterize newmolecules and materials able to degrade contaminants, to adsorbpharmaceutical remains, to obtain heterogeneous andhomogeneous catalysts to improve industrially relevant reactions.

23

Overview and goals

These efforts combined with those purveying analytical methodsdevelopment and biochemists conducting research oriented to theevaluation of their impact on human health will contribute to improvethe cleanliness of the environment.

The support of groups with expertise in computational studies,determination of properties and characterization of molecules andmaterials will significantly improve the knowledge needed to live in aClean Environment, one condition at the heart of the idea of HealthyAgeing!

These potentialities will lead to the creation of environment-friendlyand decontamination technologies, new methods for decontaminationcontrol and residual hazard assessment, and for evaluation of theirimpact on human health.

Chemistry and Biochemistry for a Clean Environment

24

Key publications

Helical Channel Mesoporous Materials withEmbedded Magnetic Iron Nanoparticles:Chiral Recognition and Implications inAsymmetric Olefin Epoxidation, C.I.Fernandes, G. B. G. Stenning, J. D. Taylor, C.D. Nunes, P.D. Vaz, Adv. Synth. Catal., 2015,in press.

Highly enantioselective olefin epoxidationcontrolled by helical confinedenvironments, C. I. Fernandes, M. S. Saraiva,T. G. Nunes, P. D. Vaz, C. D. Nunes,, J. Catal.,2014, 309, 21-32.

Highly selective and recyclable MoO3nanoparticles in epoxidation catalysis, C. I.Fernandes, P. D. Vaz, C. D. Nunes, Appl.Catal. A: Gen., 2015, in press.

Effect of the irradiation wavelength on theperformance of nanoporous carbon as anadditive of TiO2,M. A. Andrade, A. S.Mestre, R. J. Carmona, A.P. Carvalho, C. O.Ania, Appl. Catal. A : Gen, 2015, 507, 91–98.

Electrochemical oxidation of paraquat inneutral medium, M.A.M. Cartaxo, C.M.Borges, M.I.S. Pereira, M.H. Mendonça,Electrochim. Acta, 2015, 176, 1010–1018.

Pore size matters! Helical heterogeneouscatalysts in olefin oxidation, M.S. Saraiva,C.I. Fernandes, T.G. Nunes, M.J. Calhorda,C.D. Nunes, Appl. Catal. A, 2015, 180, 130–140. IF: 3.942, Q1

Improved potentiometric and opticsensitivity of polyaniline film to dissolvedoxygen by incorporating iron-porphyrin, M.Li, I. M. Ornelas, W. Liu, Y. Niu, J. P. Correia,A. S. Viana, G. Jin,Electroanal, 2015, 27, 1-10.

Development of tertiary thioamidederivatives to recover palladium(II) fromsimulated complex chloride solutions, O.Ortet, A.P. Paiva, Hydrometallurgy, 2015,151, 33–51.

Synthesis of titanate nanofibers co-sensitized with ZnS and Bi2S3nanocrystallites and their application onpollutants removal, T.J. Entradas, J.F.Cabrita, B. Barrocas, M.R. Nunes, A.J.Silvestre, O.C. Monteiro, Mater Res Bull,2015, 72, 20-28

2014Carbon-based materials prepared frompine gasification residues foracetaminophen adsorption, M. Galhetas,A.S. Mestre, M. L. Pinto, I. Gulyurtlu, H.Lopes, A. P. Carvalho. Chem. Eng. J., 2014,240: 344

Influence of activated carbons porousstructure on iopamidol adsorption, A. S.Mestre, M. Machuqueiro, M. Silva, R. Freire,I. M. Fonseca, M. S. C. S. Santos, M. J.Calhorda, A. P. Carvalho. Carbon, 2014, 77 :607

Highly enantioselective olefin epoxidationcontrolled by helical confinedenvironments. C. I. Fernandes, M. S. Saraiva,T. G. Nunes, P. D. Vaz, C. D. Nunes. J. Catal.,2014, 309: 21

Isolation and characterization of mercury-resistant bacteria from sediments of Tagusestuary (Portugal): implications forenvironmental and human health riskassessment. N. L. L. Figueiredo, J. Canário, A.Duarte, M. L. Serralheiro, C. Carvalho. J.Toxicol. Environ. Health, Part A, 2014, 77:

155

Chemistry and Biochemistry for a Clean Environment

2015

25

Ongoing projects

CO2 Mitigation and Production of Methanol by Reforming of CH4

FCT Project PTDC/AAG-TEC/3324/2012

BIONANOMINE: Bio-synthesis of nanosized semiconductors using mine wastes as material sources and environmentally friendly applications

PTDC/AAG-TEC/2721/2012

Overcoming environmental problems associated with antifouling agents: synthesis of Nature inspired nontoxic biocides and immobilization in polymeric coatings PTDC/AAGTEC/0739/2014

Multifunctional Luminescent Spin Labile Hybrid Materials PTDC/QEQ-QIN/3414/2014

New projects- FCT 2015

LIFE-Impetus: Improving current barriers for controlling pharmaceutical compounds in urban wastewater treatment plants. LIFE 14 ENV/PT/000739

New projects- Environment Policy & Governance projects, EU 2015

Chemistry and Biochemistry for a Clean Environment

Antifouling compounds for the biofouling control in aquaculture (ECOFOULESS) OF/6923/2014/DPA/DRAPALG

MAROC – Morphology-Activity Relationship in OxidationCatalysis FCT Project EXPL/QEQ-QIN/1137/2013

Smart polymer switches for green CO2 captureFundação Gulbenkian- Estímulo à Investigação

Materiais de carbono para degradação de compostosfarmacêuticos em fase aquosa em processos avançados

CRUP Action Portugal-Spain E11/11

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Healthy Life: Molecular Interventions & Regulation Mechanisms

Overview and goals

Promotion of a healthy life and an active ageing is a societal challenge inEurope, aiming at a better quality of life and providing social and economicbenefits.

The synergies afforded by the multidisciplinary research team of CQB provideoptimal conditions to be at the forefront of this research area.

Several chemistry oriented labs are proficient in synthesizing or obtaining fromnatural sources novel molecules with potential high-value bioactive properties.On the other hand, biochemists are conducting research on the biologicalmechanisms underpinning health and disease.

The preventive and therapeutic properties of newmolecules obtained by chemists can, therefore,be investigated in the framework of the mostadvanced and updated biochemical knowledge.

Marine Natural Products

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Overview and goals

The combined efforts of several labs in this thematic line will be directedtowards the promotion of healthy habits in the general population andcatalyzing novel collaborations with the business world.

In summary, with this thematic line we aim at providing key scientificcontributions to a fast incorporation of chemical and biochemical knowledgeinto the society, thus effectively contributing to a healthier and more active life!

Salvia sclareoides, medicinal plant for the prevention of neurodegenerative impairments

Healthy Life: Molecular Interventions & Regulation Mechanisms

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2015

The extracellular matrix modulates H2O2

degradation and redox signaling inendothelial cells; A. Bagulho, F. Vilas-Boas,A.Pena, C. Peneda, F. C. Santos, A. Jerónimo,R.F.M. de Almeida, C. Real; Redox Biology;2015, 6: 454

L-Histidine Based Organoclays for theStorage and Release of Therapeutic NitricOxide, A. C. Fernandes, M. L. Pinto,F.Antunes, J. Pires, J Mater Chem B MaterBiol Med, 2015, 3, 3556-3563.

Molecular details of Isoniazide-C10 bindingto wt Mycobacterium tubercullosis KatGand to its S315T mutant, V. H. Teixeira, C.Ventura, R. Leitão, C. Ràfols, E. Bosch, F.Martins, and M. Machuqueiro, Mol. Pharm.,2015, 12, 898–909.

Raising awareness of new psychoactivesubstances: chemical analysis and in vitrotoxicity screening of “legal high” packagescontaning synthetic cathinones, A.M.Araújo, M. J. Valente, M. Carvalho, D. D.Silva, H. Gaspar, F. Carvalho, M. L. Bastos, P.G. Pinho, Arch. Toxicol., 2015, 89, 757–771.

2014

Exploiting the therapeutic potential of 8-β-D-glucopyranosylgenistein: synthesis,antidiabetic activity and molecularinteraction with IAPP and amyloid β-peptide (1-42). A. R. Jesus, C. Dias, A. M.Matos, R. F. M. de Almeida, A. S. Viana, F.Macedo, R. T. Ribeiro, M. P. Macedo, C.Airoldi, F. Nicotra, A. Martins, E. J. Cabrita, J.Jiménez-Barbero, A. P. Rauter; J. Med.Chem.; 2014, 30: 9463

A biomimetic platform to study theinteractions of bioelectroactive moleculeswith lipid nanodomains. J. T. Marquês, A. SViana, R. F. M. de Almeida. Langmuir, 2014,30:12627.

Cellular polarity in aging: role of redoxregulation and nutrition. H. Soares, H.SMarinho, C. Real, F. Antunes. Genes Nutr.,2014, 9: 371

Marketed marine natural products in thepharmaceutical and cosmeceuticalindustries: tips for success. A. Martins, H.Vieira, H. Gaspar, S. Santos. Mar. Drugs,2014, 12: 1066

Design, synthesis and biological evaluationof novel isoniazid derivatives with potentantitubercular activity. F. Martins, S. Santos,C.Ventura, R. Elvas-Leitão, L. Santos, S.Vitorino, M. Reis, V. Miranda, H. F. Correia, J.Aires-de-Sousa, V. Kovalishyn, D.A.R.S.Latino, J. Ramos, M. Viveiros. Eur. J. Med.Chem., 2014, 81: 119

Key publications

Healthy Life: Molecular Interventions & Regulation Mechanisms

29

New projects- FCT 2015

Sphingolipid organization in the plasma membrane of Saccharomyces cerevisiae. Implication in antifungal mode of action and fungal resistance.

PTDC/BBB-BQB/6071/2014

Biomimetic/nanobioconjugates flexible platforms for sensitive immunosensing PTDC/CTM-NAN/0994/2014

CpHMD-L simulations of pHLIP peptides: design of new tumor-targeted drug delivery systems PTDC/QEQ-COM/5904/2014

Anion transmembrane transport promoted by drug-like molecules: building a library of anion carriers inspired in Ataluren (PTC124)

PTDC/QEQ-SUP/4283/2014

Personalised ICT Supported Service for Independent Living and Active Ageing,FP7-ICT-2013-10, Project Nr. 610359, 2013 - 2016

Diagnostic and Drug Discovery Initiative for Alzheimer’s Disease, FP7-PEOPLE-2013-IAPP, Project Nr. 612347, Industry-Academia Partnerships andPathways (IAPP), 2014 – 2018

Healthy ageing with innovative functional foods/leads for degenerative andmetabolic diseases (INOVAFUNAGEING), approved in the “Invitation forCommitments to the Strategic Implementation Plan of the European InnovationPartnership on Active and Healthy Ageing (EIP AHA) – Action A3”, 2012-2015

Ongoing projects - European Projects, Commitments and QREN

Healthy Life: Molecular Interventions & Regulation Mechanisms

30

31

32

Adsorption and Adsorbent Materials

The main goal of the Adsorption and Adsorbent Materials(AAM) group is to develop porous materials and exploretheir potentialities as adsorbents, catalysts or catalystssupports or as matrixes for drug delivery systems.Different products are under study, e.g. carbon materialswhich are usually obtained from sub products ofagricultural or industrial activities or by templatemethodologies; natural-clay based solids and metal-organic frameworks. Polyurethane matrixes with differentcompositions, and physical properties (e.g.hydrophobicity), are also developed to be used assupporting adsorbent materials.

Applications of these porous materials include theseparation of alkenes from alkane/alkene mixtures, thepurification (upgrade) of biogas and natural gas byremoving carbon dioxide and nitrogen. Special interest hasbeen given to the use of carbon materials as adsorbentsfor the removal of emergent pollutants (e.g.pharmaceutical compounds) from water.

Additionally, functionalization of porous materials withtransition metal complexes using different methodologiesfor encapsulation is a an hot topic within AAM group. Themain goal is to obtain heterogeneous complexes which arecatalytic active in the homogeneous phase.

Regarding catalysis the group has also interests in themodification of zeolites structures aiming the

improvement of their performance in refining andpetrochemical processes as well as catalysts supports

In the drug delivery systems frame, adsorption and releaseof nitric oxide was evaluated, by storing this compound inporous materials aiming a slow release which could bevery helpful for therapeutic applications.

SAPOhttp://adsorption.fc.ul.pt/

33

Highlight

MesoporosityIntracrystalline Intercrystalline

Hierarchical Zeolites

Zeolites are crystalline materials with a wide range of applications, especially asheterogeneous catalysts. However, the microporous nature of these materials limitsits application in the presence of large molecules with industrial interestThe development of hierarchical zeolites (micro + mesopores) aims to increasemolecular diffusion and the access to the active sites, extending the range ofapplication for these materials in refining, petrochemistry and fine chemistryreactions.

Modification of MCM-22 zeolite through sequential post-synthesis treatments. Implications on the acidic and catalytic behaviour, V. Machado, J. Rocha, A.P. Carvalho, A. Martins, Appl. Catal., A: Gen, 2012, 445, 329-338.

Hierarchical zeolites to higher performance catalysts

34

From biomass to carbon materials to enhance water treatment technologies

Water contamination with pharmaceutical compounds is a reality worldwide andscientists and governmental entities consider that this kind of contamination mayrequire legislative intervention. In fact, pharmaceutical compounds appear in aWatch List in the 2013/39/EU directive and, for now, activated carbons which arenon-specific adsorbents, appear as the best available decontamination technologyfor the removal of the pollutants that have a recalcitrant behaviour in conventionalwater treatment plants.The biomass-derived activated carbons developed in the Adsorption and AdsorbentMaterials group of CQB outperform commercial samples in the ability to removeeven the most recalcitrant pharmaceuticals from water.

Processo de produção de carvão activado a partir de material de cortiçaS.P.Martins, A.S. Mestre, A.P. Carvalho and P.B. Correia, 2012., PT 106637 B, Portugal.

Chars from gasification of coal and pine activated with K2CO3: Acetaminophen and caffeineadsorption from aqueous solutions, M.Galhetas, A.S.Mestre, M.L. Pinto, I. Gulyurtlu, H.Lopes and A.P. Carvalho, J. Colloid Interface Sci., 2014, 433, 94-103.

Sustainable activated carbons prepared from a sucrose-derived hydrochar: remarkableadsorbents for pharmaceutical compounds., A.S. Mestre, E. Tyszko,M.A. Andrade, M.Galhetas, C. Freire and A.P. Carvalho, RSC Adv, 2015, 5 (25), 19696-19707.

Highlight

35

Materials for storage and slow release of therapeutic gases

Nitric oxide (NO) is a small endogenous molecule with particularly interesting effectson biological systems, despite its toxicological potential. The delivery of nitric oxide incontrolled amounts to the human body is an attractive therapeutic alternative for alarge number of pathologies. NO is involved in neurological functions in synapticplasticity, neurotransmission, learning, and memory, in addition to having a primaryrole in non-specific immunity and platelet aggregation inhibition.NO is a gas at room temperature and pressure, unlike more common drug moleculesthat are usually in a solid or liquid state. Because of the limited utility of genuine NOgas in many experimental systems and the short half-life of NO in vivo, compoundsthat have the capacity to release NO have been researched. More recently,nanoporous materials were explored for their ability to act as NO delivery platforms,particularly for topical applications in dermatology, wound healing, and organconservation.

L-Histidine Based Organoclays for the Storage and Release of Therapeutic Nitric Oxide, A.C.Fernandes, M.L. Pinto, F. Antunes, J. Pires, J Mater Chem B Mater Biol Med, 2015, 3, 3556-3563

Cu2+ and Co2+ Microporous Titanosilicate ETS-4 for Storage and Slow Release of TherapeuticNitric Oxide, M.L. Pinto, A.C. Fernandes, J. Rocha, A. Ferreira, F. Antunes, J. Pires, J MaterChem B Mater Biol Med, 2014, 2, 224-230

Slow Release of NO by Microporous Titanosilicate, M.L.Pinto, J. Rocha, J.R.B. Gomes, J.Pires, Journal of the American Chemical Society, 2011, 133, 6396–6402

Highlight

36

Based on a sustainable model, starting from sugars orfrom natural resources towards new drug candidates /functional food ingredients for pharmaceutical / foodindustries, the Carbohydrate Chemistry Group aims toprovide economic and social benefits in termsof prevention of functional decline and ageing, nutrition,health and biosecurity.

Strategic areas:• New approaches towards healthy ageing included in

the activities of the European Innovation Partnershipon Active and Healthy Ageing Action Plan 3 onprevention of functional decline• Sustainable Chemistry for Functional Molecules• Therapeutics and mechanisms of action

Research is based on:Generation of new molecular entities by:• Design and synthesis• Environmentally friendly methodologies• Isolation from natural resources (plants, algae) and

structure elucidation

Polyphenols chemistry and society• Functional foods• Biomass residues valorization• Cultural heritage

Challenges:• New leads for degenerative (cancer) and amyloid

diseases (Alzheimer's disease, diabetes)• Sugar-based bactericides towards biosecurity• Functional foods for a healthy ageing

Carbohydrate Chemistry

http://carbohydrate.cqb.fc.ul.pt/

37

Highlight

Key structural featuresfor the bioactivity

Potent and selectiveBChE inhibitorRauter et. al. Bioorg.Med. Chem. 2009,17(14), 5106

New synthetic approaches for bicyclic sugars

Stereoselective reactionsWittig olefination as key stepOlefin stereocontrol based on sugar protectionReaction regiocontrol based on solvent selection

Structure optimization for bioactivity

Colaborations:

ProjectsDiagnostic and Drug Discovery Initiativefor Alzheimer's DiseaseFP7-PEOPLE-2013-IAPP

Total synthesis and stereochemicalelucidation of Miharamycins A and B.Carbohydrate-based generation ofanalogues and bioactivity studiesPOCI/PPCDT/QUI/59672/2004

Fellowships“New synthetic strategies and structural optimization of the sugar moiety from a selective butyrylcholinesterase inhibitor” SFRH/BD/90359/2013

Alzheimer’s DiseaseSelective inhibitor of BChERauter et. al. Org. Biomol. Chem. 2014,12,2446Rauter et. al. Eur. J. Org. Chem. 2014, 13, 2770

Rauter et. al. Eur. J. Med. Chem. 2015, 90, 595CANCER

38

HighlightPotential nucleotide mimetics

A-B: Nucleoside analogsB-C: Potential sugar phosphate mimetics

Synthesis

In silico potential to inhibit cyclin-dependentkinase-2 (CDK-2)

Carbonic anhydrase II:

Ki = 9.5 µM

AChE:

Ki = 11.9 μM

Biological evaluation

• New nucleotide‐like derivatives intended to inhibit disease‐associated enzymespossessing catalytic sites binding either nucleotides or functional groups mimickingpartial structures contained in nucleotides.• Efficient synthetic approaches for molecules based on new structural frameworks

for nucleoside/nucleotide mimicry.• Biological targets focused: CDKs, cholinesterases and carbonic anhydrases

Triazole-containing carbohydrate mimetics: synthesis and biological applications, N. MXavier, S. D. Lucas. In Targets in Heterocyclic Systems: Chemistry andProperties, 2014, 18, 214-235, Italian Society of Chemistry, Rome, Italy.

Preparation of a tosylhydrazidyl N-glycosyl derivative of D-glucuronic acid via tosylhydrazone formation and intramolecular ring closure, N. M. Xavier. In Comprehensive Organic Chemistry Experiments for the Laboratory Classroom , 2015, Royal Society of Chemistry, accepted for publication.

Collaborations: Palacký University & AS CR

(Czech Republic); Universität Halle-Wittenberg,

Faculdade Farmácia UL

39

Highlight

Patent Sugar derivatives having tensioactive and antimicrobial activity A. P. Rauter et al. WO 2012095792 A1

(submission: 10-01-2012, pub. date: 19-07-2012)

ProjectsNew drugs from sugars against infection caused by pathogenic

Bacillus species (FACIB), QREN Diagnostic and Drug Discovery Initiative for Alzheimer's Disease,

FP7-PEOPLE-2013-IAPP

In collaboration with:

Funded by:

| Tackling antimicrobial resistance and BiosecurityINFECTIONAntimicrobial resistance is anincreasingly serious threat to globalpublic health as new resistancemechanisms emerge and spread globally.

Dodecyl glycoside displaying selective antimicrobial activity against Bacillus anthracis and Bacillus cereus (25 µM)

Research on new antibacterialagents with new mechanismsof action is becoming urgent.

A.P. Rauter, et al., Carbohydr. Res.2005,340 (2), 191

Alkyl deoxy glycosides also significantly inhibit Enterococcus faecalis; Surface properties showed that headgroup structure is determinant for the aggregation/adsorption balance.

A.P. Rauter et al., Bioorg. Med. Chem. 2008,16 (7), 4083.

• Generation of a small library of deoxy hexopyranosides against Bacillus species • Tuning alkyl glycoside bioactivity through structural features

(D,L series), deoxygenation pattern and anomeric configuration. Surface activity is necessary but not sufficient for antimicrobial activity. Compounds target cell membrane acting with a new mechanism of action

A.P. Rauter et al., Eur. J. of Org. Chem. 2013, 1448.

A multidisciplinary project involving organic synthesis, physical chemistry,computational chemistry, biophysics and biology for the generation of a new familyof antibiotics with a new mechanism of action

40

HighlightGenista tenera for diabetes and Alzheimer´s disease prevention

EtOAcextract

8-β-D-glucosylgenistein, the main component of the EtOAc extract: Is not toxic towards human lymphocytes

Normalizes blood glucose levels of STZ-induced diabetic Wistar rats

Increases glucose-induced insulin secretionInhibits human islet amyloid polypeptide (hIAPP) fibrillization

Interacts with Amyloid β 1-42 (Aβ1-42 )polypeptides Exhibits a common binding epitope to both hIAPP and Aβ1-42

Genista tenera is a plant endemic to Madeira Island and isused in traditional medicine to control diabetes.

O

HO

OHO

OH

OH O

OH

H

HO

OH

Projects:• New antidiabetic agents from Genista tenera: Isolation, structural

characterization, synthesis and mechanisms of action, funded by FCT• From a multitarget antidiabetic glycosyl isoflavone towards new molecular

entities against Diabetes and Alzheimer’s disease: generation of lead seriesand target assessment, PhD grant funded by FCT

• Diagnostic and Drug Discovery Initiative for Alzheimer’s Disease” Industryand Academia Partnerships and Pathways (IAPP); FP7-PEOPLE-2013-IAPP

• PERsonalised ICT supported Service for Independent Living and ActiveAgeing”, FP7-ICT-2013-10

Advanced lead molecules for diabetes

A new source of functional food ingredients

Bridging nature and technologycarbohydrates and polyphenols

41

Salvia sclareoides for neurodegenerative disease prevention

Highlight

S. sclareoides extracts

potent inhibition of

acetylcholinesterase (AChE), the

enzyme that hydrolizes the

neurotransmitter acetylcholine

A. P. Rauter et al., Fitoterapia 2007, 78, 474

AChE inhibition is a standard therapy to treat patients with Alzheimer’s disease (AD) (e.g. donepezil, rivastigmine, galantamine). A new binding site of AChE for the major component rosmarinic acid (binding site B) was discovered

Rosmarinic acid also interacts with Aβ1-42. Aromatic protons are mostly involved in the binding

S. sclareoides interacts also with AD toxic oligomers, removes

amyloid fibrils to form amorphous aggregates, and prevents normal

Prion protein to convert to Prion infectious isoform

S. sclareoides is a non-

toxic aromatic herb

used in folk medicine

to treat memory loss

A. P. Rauter, et al, Chem. Eur. J. 2013, 19, 6641

A. P. Rauter, et al, Food Chem 2012, 132(4), 1930

In collaboration with:

A. P. Rauter et al, Chem Asian J. 2013, 8, 596

Projects:

Diagnostic and Drug Discovery Initiative for Alzheimer's Disease, Industry-Academia

Partnerships and Pathways (IAPP), FP7-PEOPLE-2013-IAPP

Study of Salvia species crop production aiming at the evaluation of their constituents for

the potential control of Alzheimer's disease, funded by FCT

42

Highlight

Nutrition literacy

Challenges and solutions for the prevention of frailty

Multimodal service (screening, monitoring and training services) containingnutrition, physical and cognitive modules, supported by an interoperable ICTinfrastructure offering intelligent decision support systems and gamification

Nutrition literacy

Discussing video topics and functional food ingredientswith Livia Sarkadi, EuCheMS

Executive Board, expert in Food Science

The Portuguese team: Nutriageing website

Videos: Chef is discussing with experts!

In door

Out door

Vegetable gardens growing ingredients, condiments…..

Website funding:

IUPAC 2013-054-2-300

Collaborations:INSA, Portugal Auckland University, AustraliaBudapest University of Technologyand Economics, HungaryUniversity Milano Bicocca, ItalyNetworking within FCUL andCQB groups

43

44

The main long-term objective of the Environmental andBiological Mass Spectrometry group is to explore thepotentialities of advanced mass spectrometry andspectroscopy in order to investigate at molecular level, thestructure, reactivity and energetics of compounds with,mainly, environmental and biological interest.

Advanced mass spectrometry, ‘Hyphenated’, tandem MS,high resolution (FTICR MS) and spectroscopic techniques,applied to environmental, biochemical/biological,conservation and forensic sciences, enable the structuralcharacterization of compounds, even at trace level, and incomplex matrices (as for example degradation products ofemerging contaminants in the aquatic environment), ofparticular importance to the elucidation of chemical andbiochemical reaction mechanisms and to the developmentof decontamination processes encompassed in thestrategic area entitled Sustainable Chemistry forFunctional Molecules and Materials, defined for CQB.These advanced analytical capabilities are also of majorimportance and a key issue for characterization andproperties evaluation of bioactive molecules that canpotentially contribute for the development of noveltherapeutic agents and medicines and for evaluation ofthe effectiveness and safety of these molecules.

Theoretical methodologies are also applied as a supportfor rationalization of molecular ion structure, mechanismsand gas-phase thermochemistry data.

Environmental and Biological MassSpectrometry

https://www.fc.ul.pt/pt/unidade/grupo-de-espectrometria-de-massa-ambiental-e-biológica

45

Cardiovascular diseases are among the highest cause of death in EU includingPortugal. The high cholesterol level in the blood can be mentioned as being amongthe main causes of these diseases. The first and most simple action to reducecholesterol level is to decrease its ingestion in the diet. When this action is notenough, drugs start to be prescribed. Herbal teas, or infusions, used for a wide rangeof purposes can also be used to diminish cholesterol in the blood. Although thesecompounds cannot be sold with claims for health benefits, it is well known that theyare sold and consumed in order to improve people's health. Functional foods, amongwhich are herbal teas, of natural origin, have been the subject of our studies. In ourlaboratory we have long been studying “teas” from plant origin, to determine theircomposition by mass spectrometry techniques and also in what concerns their initialand final biochemical activity after the gastro-intestinal digestion. The results ofthese studies, besides highlighting the components of those mixtures, which isimportant for their quality control, also show that the infusions can have beneficialeffects to health and can be used, for example, for lowering cholesterol in thebloodstream and to facilitate the digestive process.

Studies on the molecular mechanism of cholesterol reduction by Fraxinus angustifolia,Peumus boldus, Cynara cardunculus and Pterospartum tridentatum infusions, P.L. Falé, C.Ferreira, A.M. Rodrigues, F.N. Frazão, M.L. Serralheiro, J Med Plants Res, 2014, 8, 9.

Acetylcholinesterase inhibition, antioxidant activity and toxicity of Peumus boldus waterextracts on HeLa and Caco-2 cell lines, P.L. Fale, F. Amaral, P.J. Amorim Madeira, M. SousaSilva, M.H. Florencio F.N. Frazão, M.L.M. Serralheiro, Food Chem. Toxicol., 2012, 50, 2656.

Infusions can have beneficial health effects and may be usefulfor lowering cholesterol in the bloodstream and digestive

process facilitation

Highlight

215

184179

165149

100

9291

79

0

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100

80 120 160 200 240Inte

nsi

dad

e R

elat

iva

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46

Enzymes are the core of life. It is our mission to unravelenzyme function and structure, exploring the exquisitecomplexity of life through a systems biology approach. Ourfinal goal is to shape the rules of life to our definedpurposes such as changing enzyme specificity, rewiringpathways and creating novel functional macromolecularstructures.

Our research comprises the role of protein glycation, theglyoxalase pathway and protein-protein interactionnetworks in transthyretin amyloidosis as well as a systemsbiology approach to human infectious diseases, namelyleishmaniasis and pneumococcal diseases. We are seekingenzymes and pathways towards novel therapeuticopportunities against these human pathogens.

Our tools are a combination of computational methods,mostly implemented through in house designed software,biochemical and molecular biology techniques, as well asadvanced analytic tools, including FTICR-MS, enablingresearch in metabolomics and proteomics. We arecontinuously improving these tools and expanding thescope of its applications, most notably in the field of massspectrometry, with the development of native MS, top-down proteomics and 2DFTICR-MS.

We spawned and support a biotech start-up, BioMimetx,dedicated to deliver innovative solutions for the control ofbiological proliferation, most notably, biofouling in marineenvironments.

Enzymology

http://enzymology.fc.ul.pt/

783.9355

U-20_000003.d: +MS

780.6461

784.7394

789.5214

792.6140

797.6150

800.7134

804.1625

805.7997

808.9813

810.7101

817.2572

818.8949

825.4421

831.6327

UB glycated_000002.d: +MS0

1

2

3

4

7x10

Intens.

0

1

2

3

7x10

780 785 790 795 800 805 810 815 820 825 830 m/z

779.1550

779.2461

779.3374

779.4284

779.5194 779.6106

779.7017

779.7929

779.8840

779.9754

780.0666

780.1581780.2490

U-20_000003.d: +MS

779.3362

779.4274

779.5207

779.6104

779.7019

UB glycated_000002.d: +MS0

1

2

3

4

7x10

Intens.

0

2

4

6

5x10

779.2 779.4 779.6 779.8 780.0 780.2 m/z

810.0631

810.1865

810.3109

810.4358

810.8812 811.4405 811.5645

U-20_000003.d: +MS

810.1642

810.2539

810.3454

810.4364

810.5277

810.6188810.7101

810.8012

810.8924

810.9836

811.0745

811.1662

811.2574

811.3485811.4391811.5174

UB glycated_000002.d: +MS0.00

0.25

0.50

0.75

1.00

1.25

1.50

5x10

Intens.

0

1

2

3

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810.0 810.2 810.4 810.6 810.8 811.0 811.2 811.4 811.6 m/z

47

48

Inorganic and Theoretical Chemistry

http://intheochem.fc.ul.pt/

Our group combines complementary experimental andcomputational approaches to chemistry and biochemistry.

We develop new organometallic complexes and materials(porous solids, nanoparticles and ionic liquids) to obtainnew homogeneous and heterogeneous catalysts, aiming atimproving (enantio)selectivity in industrially relevantreactions. We also immobilize bioactive compounds to getnew non-leaching bioactive polymeric materials to protectsurfaces against biofouling. Functional nanomaterials anddevices of magnetic molecules based on spin crossover toprovide polymeric, amphiphilic or nanocrystallineenvironments are being synthesized, as well as materialsfor electrochemical CO2 reduction. Bioactive naturalproducts are isolated in the quest for new drug leads fromPortuguese marine organisms. New psychoactivesubstances marketed as recreational drugs in Portugal areidentified by NMR.

We use Quantum Chemistry to study mechanisms oforganometallic reactions, to calculate the properties ofmolecules and materials in order to improvefunctionalized materials, and to understand in detail theinteractions between bioactive metal complexes andpolyoxometalate derivatives with biomolecules anmaterials. With the help of molecular modeling andsimulation, we are interested in the study of the dynamicproperties of membranes and proteins, their pH-dependence and relation with disease. Additionally, themodeling of non-conventional bonds (such as halogenbonds) in (bio)chemical systems aiming at drug design isalso pursued.

Molecules

Materials

Proteins

Membranes

49

Inorganic and Theoretical Chemistry

Experimental Approaches

Computational Studies

pH effects on membranes and proteins

Halogen bonding in

(bio)chemical systems

In siliconanobio

solutions for medicine and

materials

Mechanisms /properties of

transition metal

derivatives

The role of hydrophobic

interactions in a molecular

disease

Hybrid Materials for

selective catalytic

processes

Identify new abuse drugs by NMR to

prevent health risksIonic liquids

in biphasic catalysis with molybdenum

complexes

Antifouling molecules and materials for

biofouling prevention

Inorganic molecules and materials for energy and magnetism

Adrià Gil Maria José CalhordaMiguel MachuqueiroNuno GalambaPaulo Costa

Carla NunesElisabete SilvaHelena GasparMarta SaraivaPaulo Martinho

50

Asymmetric binuclear Ni(II) and Cu(II) Schiff base metallopolymers, S. Realista, A. S. Viana,B. P. Cardoso, A. M. B. do Rego, P. D. Vaz, A. I. Melato, P. N. Martinho, M. J. Calhorda, RSCAdv., 2015, 5, 39495.

The 2000 Nobel Prize was awarded jointly to Alan J. Heeger, Alan G. MacDiarmidand Hideki Shirakawa for the discovery that plastic is able to conduct electricityafter being conveniently modified. Since then, researchers and their groups havedeveloped efforts to find new polymeric materials with conducting properties.Our work aimed at the preparation of polymers incorporating metal ions in theirpolymeric backbone. This modification additionally confers both chemical andmorphological properties opening possibilities to fine-tune materials for targetapplications.

Metallopolymers: Engineering molecules for smart materials

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51

Non-Releasing biocidal coatings: A new strategy for biofouling prevention

Biofouling, a spontaneous colonization of surfaces in contact with water by aquaticorganisms, is a global problem in water management systems of several industrialactivities, and is responsible for serious environmental and economic consequences.For instance, its accumulation on hulls of ships can lead to drag friction increases upto 40 % and subsequent power penalties of up to 86% at cruising speed; whenoccurring in cooling circuits of power plants, it can lead to efficiency losses of about5%. The main strategy to combat this biofouling relies on chemical control. However,this strategy has revealed to be harmful for the aquatic ecosystems, mainly owing tothe ecotoxicity and cumulative effect of the applied bioactive agents. Therefore, rigidinternational regulations have been issued (BPD EU Regulation, 2012), and more areexpected to come in a near future. New strategies, which can combine moreefficiency against biofouling and non-toxic properties for the aquatic systems, aresought.Our Group developed a new antifouling environmental friendly strategy based on thecovalent bonding of biocides in polymeric coatings (e.g. silicone based). This non-releasing biocide strategy evidenced an effective biocide immobilisation, withpromising coatings’ antifouling performance, up to 6 months to date, on seawatersubmerged coated surfaces with biocidal silicone based coatings.

5 cm

6 months of exposure in Atlantic seawater (Peniche, Portugal)

With immobilised biocides Without biocides

Functionalisation process for the biocidesimmobilisation in polymeric matrixes, E.R. Silva, O. Ferreira, J. C.M. Bordado, PatentPT Nº 10809, 2015.

New Strategy to prevent adhesion of Biofouling to Coatings, E. R. Silva, O. Ferreira, J. C.M. Bordado, ShortCommunication, J. Adhesion Society of Japan, 2015, 51, 239-240.

BIOFOULING ON A SHIP HULL

BIOCORROSION ON A SHIP HULL

The problem:

The potential solution

Highlight

52

In the last decade, more than 450 new psychoactive substances (NPS) appeared inthe market of drugs of abuse. The fast dissemination of these new drugs in theinternet created an emerging need for developing new analytical methodologies fortheir rapid identification. Since May 2014, a team of researchers of FCUL, led byHelena Gaspar, researcher at the Centro de Química e Bioquímica, works incollaboration with the Laboratório de Polícia Científica da Polícia Judiciária in theidentification and quantification of NPS in products seized by the Portuguese police.Recently, this team has identified, for the first time in Europe, a new syntheticcathinone, 4F-PBP. The results have already been published in the journal ForensicScience International 2015. This outcome highlights the importance of the academiain supporting the resolution of current problems in our society, as the control of ofNPS’s trade.The work developed by the group of FCUL consists in the isolation and structuralcharacterization of NPS, by means of NMR spectroscopy and Mass Spectrometry,from products supplied by the LPC, or in their synthesis, allowing not only theirtoxicological evaluation, but also the supply of NPS standards to forensic laboratories,to be used in routine analyses.

Researchers at FCUL work with the Portuguese Police in the fight against the trade of NPS

4F-PBP (4’-fluoro--pyrrolidinobutyrophenone), a new substance ofabuse: structural characterization and purity NMR profilingH. Gaspar, S. Bronze, S. Ciríaco, C. Leal, A. Matias, J. Rodrigues, C. Oliveira,C. Cordeiro, S. Santos, Forensic Sci. Int., 2015, 252, 168-176.

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Compounds identified in seized products in Portugal.

Polylactide (PLA), a biodegradable thermoplastic polyester derived from lactic acid, isa renewable resource, currently attracting attention for applications ranging frombiomedical to food packaging and device applications. It is considered a promisingalternative to petrochemical-based plastics and the fast growth of its productioncapacity (150,000 tons/year currently) suggests it will be a high volume commoditymaterial in the near future. In collaboration with an experimental team, we used acomputational approach to calculate the energy of all the intermediates andtransition states of the full mechanism of the ring opening polymerization (ROP) oflactide catalyzed by a binuclear Zn(II) complex in mild conditions. We identified thedetermining steps and the cooperative role of the two zinc centers. Indeed, detailedknowledge of the reaction will allow the optimization of the process, namelyimproving the catalyst (cheaper, more active), and the reaction (environmentallyfriendlier).

Dinuclear Zinc–N-Heterocyclic Carbene Complexes for Either the Controlled Ring-OpeningPolymerization of Lactide or the Controlled Degradation of Polylactide Under MildConditions, C. Fliedel, D. Vila-Viçosa, M. J. Calhorda, S. Dagorne and T. Avilés, ChemCatChem,2014, 6, 1357.

Biodegradable polymers using monomers from plants

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Since the incorporation of cisplatin in chemotherapy, the interest in the application ofmetal systems in medicine has grown rapidly. One step beyond was the incorporationof phenanthroline (phen) ligand in metal complexes, these systems showingsignificant antitumoral activity. Within the interactions of coordination complexeswith DNA, intercalation is an important binding mode and the intercalative capacityof molecules is influenced by the planarity of ligand, type of donor atom, and metalcoordination geometry. Thus the aim of this work was the comprehension andrationalization of the interaction of phen with DNA strands by means ofcomputational techniques. The results showed that intercalation produces importantchanges of geometric parameters of the base pairs. For the systems containingguanine and cytosine, hydrogen bond interactions are more important than stackinginteractions, whereas for the systems with adenine and thymine these stackinginteractions become competitive. Moreover, the contribution of dispersion forces isthe most important contribution to explain the interaction. Nevertheless, thiscontribution is necessary but not sufficient to stabilize the Pauli repulsioncontribution originating between electrons of different fragments having the samespin. Thus, charge transfer contribution (small) and the electrostatic contribution(more important) play an important role to stabilize the intercalator and compensatePauli repulsion. In fact, the values of the electrostatic contribution are roughly similarto the values of the interaction energy.

How the Intercalation ofPhenanthroline Affects the Structure,Energetics, and Bond Properties ofDNA Base Pairs: Theoretical StudyApplied to Adenine-Thymine andGuanine-Cytosine Tetramers, A. Gil, M.Melle-Franco, V. Branchadell, M.J.Calhorda, J. Chem. Theory Comput.,2015, 11, 2714.

Intercalation in DNA: Small changes in the structure that become powerful for diseases

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Treatment of ionic strength in biomolecular simulations of charged lipid bilayersD. Vila-Viçosa, V. H. Teixeira, H. A. F. Santos, A. M. Baptista, M. Machuqueiro,J. Chem. Theory Comput., 2014, 10, 5483.

Biological membranes are complex systems that have recently attracted significantscientific interest. Experimental techniques are very limited in measuring the physico-chemical processes near membranes. On the other hand, computational methods arevery useful since they allow us to study the molecular details of several lipid bilayerdisorders, associated with diseases like the Barth syndrome. The presence of manycharged lipids, render these membranes sensitive to pH. The protonation states oflipids and the ion distribution close to the bilayer are two of the main challenges inbiomolecular simulations of these systems. In this work, we proposed a new methodbased on the Poisson–Boltzmann equation to estimate the ion concentration near alipid bilayer that avoids the need for neutrality at the microscopic level. This newmethodology allows for an increased realism in our molecular simulations and canhave an important contribution in future studies.

Adding realism to computer simulations of cell membranes

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Interfacial Electrochemistry

Interfacial Electrochemistry Group research is focused oninterfacial phenomena involving high performancemodified electrodes and semiconductor nanomaterials, todevelop new platforms for (photo)electrocatalytic, energyproduction, (bio)sensing and protective purposes. This isachieved by a careful and precise combination of materials(conducting polymers, self-assembled monolayers andnanostructures) and preparation methods(electrochemical, chemical coupling/adsorption,modification/sensitization).

In catalysis and sensing is extremely advantageous andchallenging to have active centres stably immobilizedpreserving their identity and function. Association ofelectrochemical and surface sensitive characterizationtechniques greatly contributes to elucidate aboutstructure, properties and reactivity relationships. Benefitsarise from the use of functionalized electrodes, sincereactive entities properties can be tailored and modulatedby electric potential application.

Additionally, the materials evaluation in energy productionand environmental remediation processes, are studied inthe IEG group. Another research line, is the evaluation ofthe effect of bioactive chemicals and proteins onbiomimetic supported lipid bilayers, mainly by highresolution imaging.

http://electro.fc.ul.pt/

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Titanate nanotubesphotosensitization

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Cholesterol : 1-decanethiol

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Electronically conducting polymers (or conducting plastics) are well knownelectrochromic materials. They undergo reversible colour modifications accordingwith the electrical potential they are submitted. On the other hand, somemetalloporphyrins like the iron-porphyrin - that we can find in hemoglobin – are verysensitive to the presence of oxygen, which induces redox transformations in themolecule. Incorporating the iron porphyrin into a polyaniline (conducting polymer)matrix, resulted in a high sensitive oxygen sensor. In a cooperative work of the Centreof Chemistry and Biochemistry from Ciências and the Chinese Academy of Sciences, anovel oxygen sensor for Biochemical Oxygen Demand assessment with dualtransduction was developed. The interaction of the dissolved gas with the porphyrinprovokes a spontaneous adjustment of the intrinsic electric potential of the polymercausing the modification of the optical properties of the material. In this way, boththe electric signal and the optical response of the polymer reflect to the presenceand amount of dissolved oxygen. The optical monitoring of the electrode isperformed by TIRIE (Total Internal Reflection Imaging Ellipsometry) which is atechnique highly sensitive to changes of the dielectric properties of the samples. Thecombined electrochemical and optical signals strongly corroborate each other,allowing the normalization of the readings in repetitive measurements using thesame modified electrode.

Organometallic/polymer matrices for highly sensitive dual electrochemical and optical assessment of

Biochemical Oxygen Demand (BOD)

Improved potentiometric and optic sensitivity of polyaniline film to dissolved oxygen by incorporating iron-porphyrin, M. Li, I. M. Ornelas, W. Liu, Y. Niu, J.P.Correia, A. S. Viana, andG. Jin, Electroanal, 2015, 27, 1 – 10.

Dual sensor optical and electrochemical response, towards O2

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The use of nanocrystalline semiconductors as photocatalysts, on the treatment ofindustrial wastewaters, has generated great interest, due to their uniquephysicochemical properties.In particular this project aims TNTs manipulation by surface sensitization processes,through the synthesis of nanocomposite materials combining titanate nanofibers(TNF) with nanocrystalline ZnS and Bi2S3, in order to obtain nanocomposite materialswith new and improved photocatalytic performances. The TNF were produced viahydrothermal synthesis and sensitized with the semiconductor nanoparticles,through a single-source precursor decomposition method. ZnS and Bi2S3

nanoparticles were successfully grown onto the TNF’s surface and Bi2S3–ZnS/TNFnanocomposite materials with different layouts. The samples’ photocatalyticperformance was first evaluated through the production of the hydroxyl radical usingterephthalic acid as model molecule. All the tested samples show photocatalyticability for the production of this oxidizing specie, very important in thephotodegradation of organic pollutants. Afterwards, the samples were investigatedfor the removal of methylene blue. Methylene blue is an industrial dye, used often asmodel pollutant in photocatalytic degradation studies. From the nanomaterialsmaterials studied, the nanocomposites with best adsorption ability were the ZnS/TNFand Bi2S3ZnS/TNF. The most promising results, for the complete pollutant removal,were obtained considering a sequential combination of an adsorption-photocatalyticdegradation process using the Bi2S3ZnS/TNF powder as a highly adsorbent andphotocatalyst material.

Titanate nanofibers co-sensitized with ZnS and Bi2S3 nanocrystallites for pollutants removal

Synthesis of titanate nanofibers co-sensitized with ZnS and Bi2S3 nanocrystallites and their application on pollutants removal, T.J. Entradas, J.F. Cabrita, B. Barrocas, M.R. Nunes, A.J. Silvestre, O.C. Monteiro, Mater. Res. Bull. 2015, 72, 20-28.

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Supported lipid bilayers (SLB) are a very useful model system of biological lipid membranes to study membrane-related phenomena, since it allows the use of a great variety of very sensitive surface techniques. In particular, if SLB are prepared on metallic surfaces, electrochemical and optical methods can be employed expanding their applications, namely on biosensing. There has been a great effort in the development of SLB on gold surfaces, though most of the studies only concern single-component or single-phase lipid systems, then failing to mimic the mammalian plasma membrane. This work results from a close collaboration with the Molecular Biophysics group and is focused on the design of planar, continuous and stable multicomponent lipid platforms on gold with distinct phase behavior. Such lipid interfaces enable to detect, with high sensitivity, redox processes of molecules interacting with membranes, such as ubiquinones, flavonoids, and cathecolamine hormones or proteins.Currently, we are developing lipid-based biointerfaces for immunosensing, which combine a number of important characteristics in a biosensor, namely: biomimetic environment, ability to block nonspecific interaction with serum proteins, a robust arrangement regarding a continuous flow of buffer solutions (even in the presence of surfactant), and high sensitivity.

A platform to study membrane nanodomains and redox processes of bioactive molecules in different lipid

environments

A Biomimetic Platform to Study the Interactions of Bioelectroactive Molecules with Lipid Nanodomains, J. T. Marquês, A.S. Viana, and R. F. M. de Almeida, Langmuir 2014, 30, 12627−12637.

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Molecular Biophysics

http://bmn.cqb.fc.ul.pt/

The main goal of our group is to advance the state-of-theart of membrane lipid domains, providing means forimproved assessment of their involvement in drugmechanisms of action, pointing directions to develop newdrugs/drug-formulations.

Biological membranes are organized into (micro)domainsconsisting of regions with different lipid and proteincomposition, properties and functions. Furthermore,several pathologies, including cancer andneurodegenerative conditions, are characterized byspecific alterations in lipid composition and hencemembrane biophysical properties. Moreover, themolecular mechanism of action of many drugs involves atsome point their effect on membrane lipid organization(the membrane-lipid therapy principle). Thus,fundamental research on membrane domains in bothphysiological and pathological situations will take place inparallel with the study of compounds that can potentiallypromote health and prevent functional decline.

Several molecular biophysical approaches are used totackle the complex interactions between these agents andbiomembranes, proteins and DNA, with potential benefitsfor society. We use design-and-synthesis approaches todevelop new compounds, bio-inspired and from naturalorigin, namely, essential oils from aromatic and medicinalplants, seeking the valorization of Portugal and CPLPcountries natural resources.

In addition, we address the following important topics:•Development of synthetic receptors for chiral resolution

of drugs and for the transmembrane transport of anions.•Research of natural pesticide for control of insect vectors

of human pathogens (e.g. malaria and dengue).

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Dengue has recurrent epidemics in Latin America and occurred recently in CapeVerde and Madeira Island. The lack of anti-viral treatment or vaccine makes thecontrol of mosquito vectors a high option to prevent virus transmission. The use ofplants for insect control has increased worldwide, with particular emphasis on searchof essential oils (EOs) obtained by hydrodistillation.The present study evaluated the potential use of Foeniculum vulgare (fennel) EO inthe control of the dengue vector Aedes aegypti.EOs isolated from fennel aerial parts collected in Cape Verde and from a commercialfennel EO of Portugal were analyzed by NMR, GC and GC-MS. trans-Anethole (32 and30%, respectively), limonene (28 and 18%, respectively) and fenchone (10% in bothcases) were the main compounds identified in the EOs isolated from fennel fromCape Verde and Portugal, respectively.The larvicidal activity of the EOs and its major constituents were evaluated, usingWHO procedures, against third instar larvae of Ae. aegypti for 24 h. Pure compounds,such as limonene isomers, were also assayed. The lethal concentrations LC50, LC90 andLC99 were determined by probit analysis using mortality rates of bioassays. A 99%mortality of Ae. aegypti larvae was estimated at 37.1 and 52.4 μL L-l of fennel EOsfrom Cape Verde and Portugal, respectively. Bioassays showed that fennel EOs fromboth countries displayed strong larvicidal effect against Ae. aegypti, the Cape VerdeEO being as active as one of its major constituents, (-)-limonene.These results suggest the potential application of fennel EO as a possible naturallarvicidal for the control of the major dengue mosquito vector.

Ecofriendly Biolarvicide for mosquito control

Larvicidal Activity Against Aedes aegypti of Foeniculum vulgare Essential Oils fromPortugal and Cape Verde, D.K.Rocha, O.Matos , M.T.Novo, A.C.Figueiredo, M.Delgado, C.Moiteiro; Nat. Prod. Commun., 2015, 10(4), 677-682.

Ae. aegypti larvae

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alteration

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A New Lipid Order: Advancing Our Knowledge on Biomembranes and Using It to Improve Human Health

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Biological membranes are generally believed to exist in a fluid regime, where a liquiddisordered (ld) phase with low lipid packing and fast lateral diffusion of moleculescoexists with a liquid ordered (lo) one displaying higher lipid packing and slightlyslower lateral diffusion.In recent years, however, our studies have challenged the dogma that another lipidphase, the gel or solid ordered phase, is not physiologically relevant, due to the veryslow lateral diffusion of its components. We have proved that gel domains arepresent in the plasma membrane of growing yeast cells through the use offluorescent probes that exhibit different fluorescence parameters in each lipid phase[1]. This finding is now supported by independent studies in other laboratories.

More recently, in an attempt to understand the formation and properties of geldomains in biomembranes, we undertook a series of experiments using a commonglycerophosphospholipid, the phosphatidylcholine (POPC) and phytoceramide, thebackbone of the complex sphingolipids found in plants and fungi, also present inseveral human tissues such as skin [2]. Our findings using fluorescent probes andliposome suspensions pointed to the formation of POPC : phytoceramidestoichiometric complexes (with stoichiometries 3:1 and 1:2) that display uniquebiophysical properties [2]. Experiments using atomic force microscopy in supportedlipid bilayers, confocal fluorescence microscopy in giant liposomes and X-rayscattering in multibilayers corroborated the supramolecular organization of the lipidsinto complexes. Interestingly, the fluorescent parameters (anisotropy and lifetimes),exhibited by fluorescent probes in liposome suspensions [2] were identical to theones obtained for living yeast cells [1], which show that the gel domains identified invivo may share important properties with the stoichiometric complexes formed in thePOPC/phytoceramide mixtures.

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Recently, our group has contributed with a hypothesis/theory paper, proposing amodel “whereby seeds comprised of oligomerised proteins and/or lipids would serveas crystal nucleation centers for the formation of diverse gel/crystallinenanodomains”, the nanodocks model [3]. Moreover, we presented a book chapter,where the literature reports pointing for the formation of highly ordered lipiddomains in vivo was critically reviewed [4]. The relevance that ordered domains mayplay in the organization and function of biomembranes, and their implication in drugmodes of action, and antidrug mechanisms of resistance, both in infectious agentsand in cancer cells, were discussed.

[1] Gel domains in the plasma membrane of Saccharomyces cerevisiae: highly ordered, ergosterol-free, and sphingolipid-enriched lipid rafts, F. Aresta-Branco, A.M. Cordeiro, H.S. Marinho, L. Cyrne, F.Antunes, R.F. de Almeida,, J.Biol.Chem., 286 (2011) 5043-5054.[2] Formation and Properties of Membrane-Ordered Domains by Phytoceramide: Role of SphingoidBase Hydroxylation, J.T. Marquês, A.M. Cordeiro, A.S. Viana, A. Herrmann, H.S. Marinho, R.F.M. deAlmeida, Langmuir, 31 (2015) 9410-9421.[3] Crystallization around solid-like nanosized docks can explain the specificity, diversity, andstability of membrane microdomain, R.F.M. de Almeida, E. Joly, s, Frontiers in Plant Science, 5(2014) 14.[4] Biomembrane Organization and Function: The Decisive Role of Ordered Lipid Domains, J.T.Marquês, C.A.C. Antunes, F.C. Santos, R.F.M. de Almeida. (2015) in A. Iglic, C. Kulkarni, M. Rappolt,eds.: Advances in Planar Lipid Bilayers and Liposomes, Vol 22, ADPLAN, UK: Academic Press, pp 65-96

Molecular Energetics

Understanding the relationships between thermochemicalinformation and the structure and dynamics of moleculesand complex molecular systems (e.g. crystals, living cells)is the main long-term objective of the MolecularEnergetics group.

The thermodynamic stability of molecules, as measured bystandard enthalpies of formation and “bond strengths”,can, for example, be rationalized by investigating therelationships between those properties and bond lengthsand angles, steric and electronic parameters, activationenergies, etc.

The energetics of intermolecular interactions regulatesphenomena such as the dissolution of a solute in a solventand the structural organization of molecules in crystals. Byprobing these interactions it is possible, for example, tounderstand many aspects of polymorphism occurrenceand to elucidate the role of solvents in chemical reactivity.Monitoring the production of heat by living organisms canalso provide important clues about their adaptation toenvironmental changes.

The research carried out at the Molecular Energeticsgroup relies on a variety of experimental techniques, suchas X-ray diffraction, microscopy, reaction and combustioncalorimetry, Calvet-drop microcalorimetry, flow-calorimetry, time-resolved photoacoustic calorimetry,differential scanning calorimetry, thermogravimetry,crystallization reactors, and Fourier transform ioncyclotron resonance mass spectrometry (FT-ICR-MS),along with quantum chemical methods and moleculardynamics simulations. The group has a long tradition ininstrument building and database development.

http://molenergetics.fc.ul.pt/

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One of the most interesting features of nanomaterials is the change inproperties that normally accompanies a decrease in particle size. Usingcalorimetric experiments and atom-atom pair potential calculations, we wereable to show, for the first time, that the stability of sodium chloride, the mostabundant salt on earth, considerably decreases (>30%) with the decrease ofthe crystal size up to the single molecule dimension. The decrease isparticularly steep for crystal sizes below 100 nm. The results furthersuggested that the cohesive energy within each crystal layer varies from site tosite, with the energy differences between adjacent sites decreasing on movingfrom the periphery to the centre of the crystal. As expected, the atoms at theoutmost surface layer exhibit the lowest cohesive energies.

Size Matters: The Stability of NaCl, the Most Abundant Salt on Earth, Considerably Changes on Entering the Nano World

Size Matters: An Experimental and Computational Study of the Influence of Particle Size on the Lattice Energy of NaCl, S. Range, C. E. S. Bernardes, R. G. Simoes, M. Epple, M. E. Minas da Piedade, J. Phys. Chem. C, 2015, 119, 4387-4396.

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The Thermochemistry of Cubane 50 Years after Its Synthesis

The Thermochemistry of Cubane 50 Years after ItsSynthesis: A High- Level Theoretical Study of Cubaneand Its Derivatives, F. Agapito, R.C. Santos, R.M.Borges dos Santos, J.A. Martinho Simões, J Phys ChemA, 2015, 119, 2998-3007.

Cubane is a unique molecule for its extraordinary C8 cage, where all the sp3hybridized carbon atoms have C–C–C bonds angles of 90°. It is therefore one of themost strained compounds known and, until its synthesis in 1964, there was doubtthat such a molecule could even hold together. But cubane turned out to be asurprisingly stable molecule, since no kinetically viable paths exist for its thermaldecomposition. The synthesis of cubane was driven by the curiosity and fascinationof organic chemists in obtaining the molecular equivalent of a platonic solid.Nevertheless, its derivatives have many important potential applications, such as inhigh-energy fuels, explosives and propellants (e.g., octanitrocubane), and as anintermediates in pharmaceutical preparations. Because the cubane frame is rigid,substituents will have precise spatial relationships to each another. This offersfascinating substituent positioning possibilities for the synthesis of novelpharmaceuticals. To assess viable synthetic pathways, knowledge on the energeticsof the cubane molecule and its reactive intermediates is needed. In general, thiskinetic modeling requires “chemical accuracy” of about ±4 kJ mol-1. We used high-accuracy state of the art computational methods to determine the enthalpies offormation of cubane and related compounds.

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Redox Biology Group

http://redox.fc.ul.pt/

The Redox Biology group research focuses on hydrogenperoxide (H2O2), the main cellular oxidant now considereda key redox regulator. The long-term goal is to understandsignalling pathways and molecular mechanisms by whichH2O2 regulates physiological processes that, whenunbalanced, lead to disease.

H2O2, is continuously produced intracelullarly, as a by-product of aerobic metabolism, and extracelullarly as aresult of phagocyte activation. Our group uses aninterdisciplinary approach, as the team is composed ofpeople with a strong background in molecular biology, freeradical biochemistry, cell biology and mathematicalmodeling, with a combination of both experimental andmathematical modelling approaches to study cellularredox regulation by hydrogen peroxide and itsinvolvement in physiological cellular processes and indisease.

The group expects to establish quantitative andcause/effect relationships between H2O2 levels andregulation of gene expression, organelle dynamics anddisease. These studies will allow to identify moleculartargets of H2O2 with possible therapeutic use in diseases,such as cancer and inflammation, and in aging.

In addition, we aim at assessing the biological effects ofemerging contaminants at sub-lethal concentrations. Ourefforts will be focused on the biological adaptationinduced by contaminants. For that we will use our know-how on H2O2 adaptation acquired over the last decade.

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Hydrogen peroxide (H2O2), a reactive oxygen species (ROS), is a ubiquitous oxidantpresent in all aerobic organisms. Since its first identification in a living cell, H2O2 wasconsidered a toxic by-product of aerobic metabolism, something that cells had toremove. If H2O2 detoxification catalyzed by catalases and peroxidases was notadequate, H2O2 would diffuse and oxidize biological targets causing cellularmalfunctions, i.e. oxidative stress, responsible for several pathologies and aging.Starting in the 90s this paradigm of hydrogen peroxide as toxic started to change to aparadigm where hydrogen peroxide acts in cellular regulation and is involved incellular signalling – redox signalling – through the oxidation of thiols in proteins thatact as redox sensors. Nowadays, redox biology is an established field and theessential regulating role played by H2O2 in vivo with important implications in healthand disease is unquestionable. In this work it was shown that the complexity of redoxregulation increases along the phylogenetic tree and that H2O2 modulates geneexpression at all steps from transcription to protein synthesis. Also, some of theunanswered questions regarding our understanding of redox-dependent regulationof gene expression were addressed:

What makes a good H2O2 sensor?What are the common chemical and kinetic principles that govern H2O2

signaling?Is it possible to obtain an integrative view of H2O2 regulation of transcriptionfactors?

From oxidative stress to redox biology: understanding the cellular mechanisms of redox regulation by hydrogen peroxide

Hydrogen peroxide sensing, signaling and regulation of transcription factorsH.S.Marinho, C. Real, L. Cyrne, H. Soares, F. Antunes,Redox Biol. 2014, 2, 535-562.

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Separation Science & Technology Group

The Separation Science & Technology (SS&T) group iscomposed by two research laboratories, namely, theChromatography & Capillary Electrophoresis Lab. and theHydrometallurgical Separations Lab. The common goal ofour group is the development of new approaches toimplement chemical separation techniques. The researchwork carried out by our group is based on two differentresearch lines:

The Chromatography and Capillary Electrophoresis lineinvolved on the development of new analyticalmethodologies to monitor trace levels of several classesof emergent compounds (e.g. EDC’s, PPCP’s, POP’s,DBP’s, etc.) from many type of priority matrices. Most ofour analytical work has been focused on theimplementation of novel sorption-based microextractionmethodologies in combination with modern instrumentalsystems, in particular as analytical alternatives tomonitor environmental, pharmaceutical, food, forensicand biological samples.

The Hydrometallurgical Separations line focuses researchon the development and characterization of newfunctional organic molecules to efficiently and selectivelyrecover metal species from feed industrial complexaqueous solutions, and / or effluents. One of the aims isto contribute to the decontamination of theenvironment, through innovative processes for thehydrometallurgical recycling of end-of-life materials, andprofiting from the economic value several metals inindustrial wastes have.

http://sepscitech.fc.ul.pt/

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Solid State Chemistry

The main goal of the Solid State Chemistry group is relatedto the preparation and characterization of environmental /energy / biocompatible materials with high economic andsocial benefit. Solid State Chemistry Group interests arefocused on functional inorganic materials, namely binaryand ternary oxides. These materials can be designed,tailoring its properties and improving its functionalitythrough solid state chemistry, solution chemistry,hydrothermal and/or electrochemical synthesis routes.

Applications of these materials include:

Environment protection – Development of new catalystsfor toxic pollutants and pharmaceutical drugs degradation,by means of photocatalysis or photoelectrocatalysisprocesses. The group combines different materialscomposition with specific methods of synthesis to designthe catalyst surface, which is crucial to improve thecatalytic activity.

Energy conversion – The manufacture and improvement ofphotoanodes for dye-sensitised solar cells (DSSC) is anarea where the SSC group has been working. The mainobjective of our work is the enlargement of metal oxidebased nanostructures that maximize the electrontransport, enhancing the power conversion efficiencies ofthe DSSC device, using low-cost and soft processingmethods.

Biomedicine – One of the biomedical applications ofmagnetic iron oxide nanoparticles is magnetichyperthermia for cancer therapy, a technique which allowsto destroy cancer cells, also increasing the efficiency ofchemo- or radiotherapy. Our group is particularlyinterested in the development of new biocompatiblematerials with magnetic properties suitable to make themgood candidates for magnetic hyperthermia for cancertherapy.

http://ssc.ciencias.ulisboa.pt/

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The removal of organic pollutants and pharmaceutical drugs from wastewater iscurrently one of the major concerns in environmental control. In order to addressthese problems, considerable efforts have been devoted to develop techniques moreeffective than the conventional processes to eliminate these pollutants.Removal of organic pollutants:

For the first time the growth of immobilized CaMn3O6 nanorods (NRs) by RFmagnetron sputtering onto quartz glass substrates was carried out. It was found thatthe immobilized CaMn3O6 NRs exhibit much higher photocatalytic activity than theTiO2 films on the degradation of Rh6G under visible light irradiation. This studyfurther revealed that the high catalytic efficiency of CaMn3O6 NRs probably arises asa result of the complex interaction between the double chains of edge-shared MnO6

octahedra, the mixture between Mn3+ and Mn4+, and/or the higher surface-to-volume ratio (surface morphology) afforded by the nanorods geometry, together witha process of dye self-sensitization. Furthermore, it is reported here the importance ofthis new nanostructured material in obtaining active visible-light photocatalysts.Pharmaceutical drugs degradation:

Photoactive annealed Ti/Zn-TiO2 electrodes were successfully prepared and used forthe first time on the photoelectrochemical degradation of Ibuprofen. Wedemonstrated that Ibuprofen was efficiently degraded probably due to high area ofthe films, as a consequence of their morphology: ZnO needle-shaped grains.

New materials for wastewater treatment

Hierarchically grown CaMn3O6 nanorods by RF

magnetron sputtering for enhanced visible-light-

driven photocatalysis, B. Barrocas, S. Sério, M. E.

Melo Jorge, J Phys Chem C, 2014, 118,

24127−24135.

Annealed Ti/Zn-TiO2 nanocomposites tested as

photoanodes for the degradation of Ibuprofen, A.

Gomes, T. Frade, K. Lobato, M. E. Melo Jorge, M. I.

da Silva Pereira, L. Ciriaco, A. Lopes, J. Solid State

Electr, 2012, 16, 2061-2069.

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Tailoring one-dimensional nanostructured metal oxides and their application in energy conversion technology

1 m

The general use of solar energy harvesting is still limited by two significantchallenges, conversion efficiency and cost. Among novel PV technologies, the highestefficiency was attained, up to now, with solid-state perovskite solar cells (PSC) withan overall efficiency of 20 %.The manufacture and improvement of electron-transporting materials for PSC is animportant subject which has been developed in recent years by our group,contributing to the progress of new technologies for applications in energyconversion.Our principal aim is to develop metal oxides based nanostructures that maximize theelectron transport, enhancing the power conversion efficiencies of the solar cellsdevice, using low-cost and soft processing methods, combining electrochemical-chemical deposition routes.This work is developed in straight collaboration with DEGGE/FCUL, CEFITEC/FCT/UNLand CIDETEC.

Nucleation and growth of ZnO nanorod arrays onto flexible substrates, D. Siopa, A. Gomes,J. Electrochem. Soc. 2013, 160, D476-484.

A possible growth mechanism for ZnO-TiO2 composite nanostructured films prepared byelectrodeposition, T. Frade, M. E. Melo Jorge, B. Fernández, R. Pereiro, A. Gomes, J.Electrochem. Soc. 2014, 161, D125-D133.

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Synthesis of magnetic nanoparticles for magnetic hyperthermia

Magnetic hyperthermia therapy can be a valuable aid in cancer treatment, with lessharmful side effects to the patient. It relies on the heat released by magneticnanoparticles under the influence of an alternate magnetic field. Magnetite (Fe3O4)and maghemite (-Fe2O3) are by far the most explored nanoparticles forhyperthermia applications, but other ferrites, nanocomposites and core@shellstructures are also being investigated, in order to improve their ability to act as nano-heaters, making them useful for magnetic hyperthermia.The Solid State Group from CQB, working in straight collaboration with BioISI -Biosystems and Integrative Sciences Institute, has been especially involved in thesearch of new synthesis and processing methods that can improve the magneticproperties of the nanoparticles. We intend to pursue this route since, in spite of thelarge efforts deployed by various research groups, the thermal efficiency ofbiocompatible nanoparticles have not yet reached the threshold required to allowregular efficient clinical use of magnetic hyperthermia.

Hyperthermia studies of ferrite nanoparticles synthesized in the presence of cotton

S.G. Mendo, A. F. Alves, L. P. Ferreira, M.M. Cruz, M.H. Mendonça, M. Godinho and M.

Deus Carvalho, New J. Chem., 2015, 39, 7182 – 7193.

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Structure and Reactivity

The major long term goal of the Structure and Reactivitygroup (SRG) is the development of rigorous and well-validated quantitative structure-property/activityrelationships (QSPR/QSAR) to interpret and predictbiological and physicochemical phenomena, as well as toassist in the design, synthesis and assessment of newmolecules.

The group’s expertise in structural characterization ofeither newly synthesized molecules (designed on the basisof various QSAR methodologies) or of isolated compoundsfrom natural sources (e.g., marine invertebrates fromPortuguese exclusive waters), has also been focusedon the evaluation of antimicrobial activities, in particularantitubercular activities against wild and resistant strains,or on the identification of new leads to target cancer andCentral Nervous System disorders (e.g., IDO, β-amyloidand TAU proteins), within the scope of severalcollaborations.

Also central to the group’s work is the structural andphysicochemical characterization of conventional and/ornon-conventional solvents and their mixtures, for solventtuning in dynamic and equilibrium processes, in view ofgreener future applications in synthetic, separation and/orCO2 capture processes.

SRG integrates researchers with diverse backgrounds andskills ranging from Physical to Organic Chemistry. It has aconsolidated know-how in spectroscopic characterization,in the study of solute and solvent effects and in theaccurate evaluation of kinetic, thermodynamic, interfacialand solvatochromic properties, as well as in the use ofstatistical and machine learning techniques such asMultiple Linear Regressions and Neural Networks.

http://structreact.fc.ul.pt/

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Molecular details of INH-C10 binding to wt KatG and to its S315T mutant, V. H. Teixeira, C.Ventura, R. Leitão, C. Rafols, E. Bosch, F. Martins, M. Machuqueiro, Mol. Pharmaceutics,2015, 12, 898.

Isoniazid (INH) is still one of the two most effective antitubercular drugs and isincluded in all recommended multitherapeutic regimens. Because of the increasingresistance of Mycobacterium tuberculosis to INH, new INH-based compounds havebeen proposed to circumvent this problem. The KatG enzyme is known to activateINH, leading to a potent antitubercular drug. The S315T enzyme mutant is verycommon and interferes with this “drug production” process. In this work, we presenta detailed comparative molecular study of the interactions between the normalenzyme or its S315T mutant form and either INH or INH-C10, a new acylated INHderivative. Our results indicate that the aliphatic tail in INH-C10 brings the compoundcloser to the active site. INH-C10 is able to counterbalance most of theconformational restrictions introduced by the mutation, which are thought to beresponsible for the decrease in INH activity in the mutated strain. Therefore, INH-C10appears to be a very promising lead compound and a new hope against tuberculosis.

Unraveling antitubercular drug activities using in silico approaches

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Thermochemistry of 1-alkylimidazolesJ. Vitorino, F. Agapito. C. E. S. Bernardes, M. E. Minas da PiedadeJ. Chem. Thermodyn., 2015, 80, 59-64. IF 2.679, Q1

Size Matters: An Experimental and Computational Study of theInfluence of Particle Size on the Lattice Energy of NaClS. Range, C. E. S. Bernardes, R. G. Simoes, M. Epple, M. E. Minas daPiedadeJ. Phys. Chem. C 2015, 119, 4387-4396. IF: 4.772, Q1

Gas Phase Affinity Scales for Typical Ionic Liquid Moieties byCooks Kinetic MethodJ. Vitorino, J. P. Leal, M. E. Minas da PiedadeChemPhysChem 2015, 16, 1969-1977. IF: 3.419, Q1

Benchmark Thermodynamic Properties of Methylanisoles:Experimental and Theoretical StudyV. N. Emel yanenko, K. V. Zaitseva, F. Agapito, J. A. MartinhoSimões, S. P. VerevkinJ. Chem. Thermodyn., 2015, 88, 155-162. IF: 2.679, Q1

The Thermochemistry of Cubane 50 Years After Its Synthesis: AHigh-Level Theoretical Study of Cubane and Its DerivativesF. Agapito, R. C. Santos, R. M. Borges dos Santos, J. A. MartinhoSimões,J. Phys. Chem. A, 2015, 119, 2998-3007. IF: 2.693, Q2

Evaluation of the OPLS-AA Force Field for the Study of Structuraland Energetic Aspects of Molecular Organic CrystalsC. E. S. Bernardes, A. JosephJ. Phys. Chem. A, 2015, 119. 3023-3034. IF: 2.693, Q2

Kinetics and Mechanism of the Thermal Dehydration of a Robustand Yet Metastable Hemihydrate of 4-Hydroxynicotinic AcidA. Joseph, C. E. S. Bernardes, A. S. Viana, M. F. M. Piedade, M. E.Minas da PiedadeCryst. Growth Des. , 2015, 15, 3511-3524. IF: 4.891, Top 5%

Benchmark Thermochemistry of Methylbenzonitriles:Experimental and Theoretical StudyK.V. Zaitseva, V.N. Emel'yanenko, F. Agapito, A.A. Pimerzin, M.A.Varfolomeev, S.P. Verevkin,J. Chem. Thermodyn., 2015, 91, 186-193. IF: 2.679, Q1

Assessment and comparison of the properties of biodieselsynthesized from three different wet microalgae biomassK. N. Gangadhar, H. Pereira, H. P. Diogo, R. M. Borges dos Santos,B. L. A. P. Devi, R. B. N. Prasad, L. Custódio, F. X. Malcata, J. Varela,L. BarreiraJ. Appl. Phycol. (in press). IF: 2.559, Q1

Molecular details of INH-C10 binding to wt KatG and to its S315TmutantV. H. Teixeira, C. Ventura, R. Leitão, C. Ràfols, E. Bosch, F. Martins,and M. MachuqueiroMol. Pharm., 2015, 12, 898–909. IF: 4.384, Q1

Constant-pH molecular dynamics study of kyotorphin in anexplicit bilayerP. R. Magalhães, M. Machuqueiro, A. M. BaptistaBiophys. J., 2015, 108, 2282–2290. IF: 3.972, Q1

Constant-pH MD simulations of an oleic acid bilayerD. Vila-Viçosa, V. H. Teixeira, A. M. Baptista, M. MachuqueiroJ. Chem. Theory Comput., 2015, 11, 2367–2376. IF:5.498, Q1

Raising awareness of new psychoactive substances: chemical analysis and in vitro toxicity screening of “legal high” packages contaning synthetic cathinonesA.M. Araújo, M. J. Valente, M. Carvalho, D. D. Silva, H. Gaspar, F. Carvalho, M. L. Bastos, P. G. PinhoArch. Toxicol., 2015, 89, 757–771. IF: 5.980, Q1

Determination of mitragynine in urine matrices by bar adsorptive microextraction and HPLC analysisN. R. Neng, S. M. Ahmad, H. Gaspar, J.M.F. NogueiraTalanta, 2015, 144, 105–109., IF: 3.545, Q1

The antimicrobial activity of heterotrophic bacteria isolated from the marine sponge Erylus deficiens (Astrophorida, Geodiidae)A.P. Graça , F. Viana, J. Bondoso, M. I. Correia, L. Gomes, M. Humanes, A. Reis, J. R. Xavier, H. Gaspar, O. M. LageFront Microbiol., 2015, 6, article 389, 1–14. IF: 3.989, Q1

4F-PBP (4’-fluoro--pyrrolidinobutyrophenone), a new substance of abuse: structural characterization and purity NMR profiling H. Gaspar, S. Bronze, S. Ciríaco, C. Leal, A. Matias, J. Rodrigues, C. Oliveira, C. Cordeiro, S. Santos, Forensic Sci. Int., 2015, 252, 168–176. IF: 2.140, Q1

Pore size matters! Helical heterogeneous catalysts in olefin oxidationM.S. Saraiva, C.I. Fernandes, T.G. Nunes, M.J. Calhorda, C.D. NunesAppl. Catal. A, 2015, 180, 130–140. IF: 3.942, Q1 Top 10

Molybdenum(II) catalyst precursors in olefin oxidation reactionsC.D. Nunes, M. J. CalhordaInorg. Chim. Acta, 2015, 431, 122–131. IF: 2.046, Q2This article belongs to a special issue: Advances in Transition Metal Catalysis, Edited By Maurizio Peruzzini and Maria Caporali

Vanadyl cationic complexes as catalysts in olefin oxidationC. D. Nunes, P. D. Vaz, V. Félix, L. F. Veiros, T. Moniz, M. Rangel, S. Realista, A. C. Mourato, M. J. CalhordaDalton Trans. 2015, 44, 5125–5138. IF: 4.197 Q1

How the Intercalation of Phenanthroline Affects the Structure, Energetics and Bond Properties of DNA Base Pairs. Theoretical Study Applied to Adenine-Thymine and Guanine-Cytosine TetramersA.Gil, V. Branchadell, M.J. CalhordaJ. Chem. Theory Comput., 2015, 11, 2714–2728. IF:5.498, Q1

Fe(III) SalEen derived SchIff base complexes as potential contrast agentsB. P. Cardoso, A. I Vicente, J. B. J Ward, P. J. Sebastião, F. V. Chávez, S. Barroso, A. Carvalho, S. J. Keely, P. N.Martinho, M. J. CalhordaInorg. Chim. Acta, 2015, 432, 258–266. IF: 2.046, Q2

Asymmetric Binuclear Ni(II) And Cu(II) SchIff Base MetallopolymersS. Realista, A. S. Viana, B. P. Cardoso, A. M. Botelho do Rego, P. D. Vaz, A. I. Melato, P. N. Martinho, M. J. CalhordaRSC Adv., 2015, 5, 39495–39504. IF: 3.840, Q1

Catalytic activity of Mo(II) complexes in homogeneous and heterogeneous conditionsM. V. Dias, M. S. Saraiva, P. Ferreira, and M. J. CalhordaOrganometallics, 2015, 34, 1465–1478. IF: 4.126, Q1

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Comparing spectroscopic and electrochemical properties ofcomplexes of type [Cp’M(η3-C3H5)(CO)2] (Cp’ = Cp, Ind, Flu;M=Mo, W): a complementary experimental and DFT studyS. Gonçalves, L. F. Veiros, C. A. Gamelas, C. Cabrita, M. J. Calhorda,C. F.G.C. Geraldes, J. Green, E. Packham, M. G. B. Drew, V. Félix, A.G. Santos, C. C. RomãoJ. Organomet. Chem., 2015, 792, 154-166. IF: 2.173, Q1Special issue: Concepts for the Structure and Bonding inOrganometallic Compounds, Ed. Richard Adams and ThomasStrassner

Luminescent Di- and Trinuclear Boron Complexes Based onAromatic Iminopyrrolyl Spacer Ligands: Synthesis,Characterization and Application in OLEDsD. Suresh, C. S. B. Gomes, P. S. Lopes, C. A. Figueira, B. Ferreira, P.T. Gomes, R. E. Di Paolo, A. L. Maçanita, M. T. Duarte, A. Charas, J.Morgado, D. Vila-Viçosa, M. J. CalhordaChem. Eur. J., 2015, 21, 9133–9149. IF: 5.731, Q1

Synthesis and Reactivity of Taddol-Based Chiral Fe(II) PNP PincerComplexes -Solution Equilibria between ĸ2 P,N- and ĸ3 P,N,P-Bound PNP Pincer LigandsC. Holzhacker, B. Stöger, M. D. Carvalho, L. P. Ferreira,E.Pittenauer, G. Allmaier, L. F. Veiros, S. Realista, A. Gil, M. J.Calhorda, D. Müller, K. KirchnerDalton Trans., 2015, 44, 13071–13086, IF: 4.197 Q1

Preference for sulfoxide S- or O-bonding to 3d transition metals –DFT insightsB.P. Cardoso, B. Royo, M. J. CalhordaJ. Organomet. Chem., 2015, 792, 167-176. IF: 2.173, Q1Special issue: Concepts for the Structure and Bonding inOrganometallic Compounds, Ed. Richard Adams and ThomasStrassner

Highly selective and recyclable MoO3 nanoparticles inepoxidation catalysisC. I. Fernandes, P. D. Vaz, C. D. NunesAppl. Catal. A: Gen., 2015, in press. IF: 3.942, Q1

MoO2 nanoparticles as highly efficient olefin epoxidationcatalystsA.Bento, A. Sanches, E. Medina, C. D. Nunes, P. D. VazAppl. Catal. A: Gen., 2015, in press. IF: 3.942, Q2

L-Histidine Based Organoclays for the Storage and Release ofTherapeutic Nitric OxideA. C. Fernandes, M. L. Pinto, F.Antunes, J. PiresJ Mater Chem B Mater Biol Med, 2015, 3, 3556-3563. IF: 6.1, Q1

Understanding Gas Adsorption Selectivity in IRMOF-8 UsingMolecular SimulationR.S. Pillai, M. L. Pinto, J. Pires, M. Jorge, J. R. B. GomesACS Appl. Mater. Interfaces, 2015, 7, 624-637. IF: 6.723, Q1

Simple Analysis of Historical Lime MortarsJ. PiresJ. Chem. Educ., 2015, 92, 521–523. IF: 1.106, Q3.

Adsorption of a Textile Dye on Commercial Activated Carbon: ASimple Experiment to Explore the Role of the Surface Chemistryand Ionic StrengthA. Martins, N. NunesJ. Chem. Educ., 2015, 92, 143-147, IF: 1.106, Q3

Sustainable activated Carbons prepared from a Sucrose derived Hydrochar: Remarkable Adsorbents for Pharmaceutical CompoundsA.S. Mestre, E. Tyszko, M.A. Andrade, M. Galhetas, C. Freire, A.P. CarvalhoRSC Adv., 2015, 5, 19696-19707, IF: 3.84, Q1

New antitumor 6-chloropurine nucleosides inducing apoptosis and G2/M cell cycle arrestS. Schwarz, B. Siewert, , R. Csuk, A. P. Rauter,Eur. J. Med. Chem., 2015, 90, 595-602. IF:3.447, Q1

Self-organizing Behaviour of Glycosteroidal Bolaphiles: Insights into Lipidic MicrosegregationR. Xu, F. A. li-Rachedi, N. M. Xavier, S. Chambert, F. Ferkous, Y. Queneau, S. J. Cowling, E. J. Davis, J. W. Goodby, Org. Biomol. Chem., 2015, 13, 783–792. IF: 3.562 Q1

Improved potentiometric and optic sensitivity of polyaniline film to dissolved oxygen by incorporating iron-porphyrinM. Li, I. M. Ornelas, W. Liu, Y. Niu, J. P. Correia, A. S. Viana, G. JinElectroanal, 2015, 27, 1-10. IF: 2.138, Q2

Biotechnologically obtained nanocomposites: A practical application for Photodegradation of Safranin-T under UV-Vis and solar lightJ.P. Costa, A.V. Girão, O.C. Monteiro, T. Trindade, M.C. CostaJ. Environ. Sci. Health, Part A, 2015, 50 (10), 996-1010, IF: 1.164, Q3

Recognition of bio-relevant dicarboxylate anions by an azacalix[2]arene[2]triazine derivative decorated with urea moietiesM. Santos, S. Carvalho, I. Marques, C. Moiteiro, V. Félix, Org. Biomol. Chem., 2015, 13, 3070-3085. IF: 3.562, Q1

Superoxide dismutase enzymosomes: carrier capacity optimization, in vivo behaviour and therapeutic activityM.L. Corvo, H.S. Marinho, P. Marcelino, R. Lopes, C.A. Vale, C. Marques, L.C.D. Martins, P. Laverman, G. Storm, M.B.F.MartinsPharmacol Res, 2015, 32, 91-102. IF 3.420; Q1

Electrochemical behaviour of a Cobalt-Chromium-Molybdenum dental alloy in artIficial salivas Influence of phosphate ions and mucin componentsA.Gomes, S.R. de Aguiar, M. Nicolai, M. Almeida Bio-Med Mater Eng, 2015, 25, 53–66. IF: 1.091, Q3

Non-destructive analysis of Portuguese "dinheiros" using XRF-overcoming patina constraintsS. Pessanha, M.Costa, M.I.Oliveira, M. E. M. Jorge, M.L. CarvalhoAppl Phys A-Mater, 119, 1173-1178. IF: 1.704, Q2

Use of quantitative structure–property relationships to study the solvation process of 18-crown-6M. Reis, Nelson Nunes, R. Elvas-Leitão, F. Martins.Thermochim Acta, 2015, 604, 140-144. IF: 2.184, Q2

Novel insights for permeant lead structures through in vitro skin diffusion assays of Prunus lusitanica L., the Portugal Laurel M.C. Costa, P. Duarte, N.R. Neng, J.M.F. Nogueira, F. Costa, C. RosadoJ. Mol. Struct., 2014, 1079, 327-336. IF:1.602 Q3

81

Publications

Thermodynamic Study of Aqueous 2-(Isopropylamino)ethanol. A Sterically Hindered New Amine Absorbent for CO2 captureI.M.S. Lampreia, A.F.S. Santos, M.L.C.J. Moita, L.C.S. Nobre. J. Chem. Thermodyn.2015, 81, 167-176. IF: 2.679, Q1

Activity Coefficients in the Surface Phase of Liquid MixturesM.S.C.S. Santos, J.C.R. Reis. ChemPhysChem 2015, 16, 470-475. IF: 3.419, Q1

Trends in the Hydrogen Activation and Storage by Adsorbed 3D Transition Metal Atoms onto Graphene and Nanotube Surfaces: A DFT Study and Molecular Orbital AnalysisH. Valencia, A. Gil, G.FrapperJ. Phys. Chem. C 2015, 119(10), 5506. IF: 4.772, Q1

Nematotoxic and phytotoxic activity of Satureja Montana and Ruta graveolens essential oils on Pinus pinaster shoot cultures an P. pinaster with Bursaphelenchus xylophilus in vitro co-cultures. J. M. S. Faria, I. Sena, C. Moiteiro, R. N. Bennett, M. Mota, C. Figueiredo Ind. Crop. Prod., 2015, 77, 59-65. IF: 2.837 Q1

Larvicidal Activity Against Aedes aegypti of Foeniculum vulgareEssential Oils from Portugal and Cape Verde D. K. Rocha, O. Matos, M. T. Nóvoa, A. C. Figueiredo, M. Delgado, C. Moiteiro Nat. Prod. Commun., 2015,10, 677-682. IF:0.906

Transthyretin Amyloidosis: Chaperone Concentration Changes and Increased Proteolysis in the Pathway to DiseaseG. da Costa, C. Ribeiro-Silva, R. Ribeiro, S. Gilberto, R.A. Gomes, A. Ferreira, É. Mateus, E. Barroso, A.V. Coelho, A.P. Freire, C. Cordeiro PLoS One, 2015 Jul 6;10(7):e0125392. IF: 3.234

Re(I) and Tc(I) Complexes for Targeting Nitric Oxide Synthase: Influence of the Chelator in the Affinity for the EnzymeB.L. Oliveira, M. Morais, F. Mendes, I.S. Moreira, C. Cordeiro, P.A. Fernandes, M.J. Ramos, R. Alberto, I. Santos, J. D. CorreiaChem Biol Drug Des. 2015 Apr 20. IF:2.845 Q2

Reversible lysine modification on proteins by using functionalized boronic acidsP.M. Cal, R.F.Frade, C. Cordeiro, P.M. GoisChemistry, 2015 May 26;21(22):8182-7. IF:5.731 Q1

Effect of the irradiation wavelength on the performance of nanoporous carbon as an additive of TiO2

M. A. Andrade, A. S. Mestre, R. J. Carmona, A.P. Carvalho, C. O. Ania, Appl. Catal. A : Gen, 2015, 507, 91–98. IF: 3.942 Q1

The influence of the textural properties of activated carbons on acetaminophen adsorption at different temperaturesM. Galhetas, M.A. Andrade, A.S. Mestre, E. Kangni-foli, M.L. Pinto, A.P. CarvalhoPhys. Chem. Chem. Phys., 2015, 17, 12340-12349. IF:4.493 Q1

Design, synthesis and bioevaluation of tacrine hybrids with cinnamate and cinnamylidene acetate derivatives as potential anti-Alzheimer drugs. C.Quintanova, R.S. Keri, S.M. Marques, M.G. Fernandes, S.M. Cardoso, M.L. Serralheiro, M.A. Santos MedChemComm, 2015 Advance Article. IF 2.495

Electrochemical oxidation of paraquat in neutral mediumM.A.M. Cartaxo, C.M. Borges, M.I.S. Pereira, M.H. MendonçaElectrochim. Acta, 2015, 176, 1010–1018, IF 4.504 Q1

Spin transition in arrays of gold nanoparticles and spin crossover moleculesJ. Devid, P. N. Martinho, M. V. Kamalakar, Ú. Prendergast, J-F. Dayen, V. Meded, T. Lemma, R. González-Prieto, F. Evers, T. E. Keyes, M. Ruben, B. DoudinACS Nano, 2015, 9, 4496–4507. IF: 12.881 Q1

Formation and properties of membrane ordered domains by phytoceramide: role of sphingoid base hydroxylationJ. T. Marquês, A. M. Cordeiro, A. S. Viana, A. Herrmann, H. S. Marinho, R. F. M. de Almeida Langmuir, 2015, 31, 9410 9421. IF:4.457 Q1

The extracellular matrix modulates H2O2 degradation and redox signaling in endothelial cells. A. Bagulho, F. Vilas-Boas, A. Pena, C. Peneda, F. C. Santos, A. Jerónimo, R. F. M. de Almeida, C. Real Redox Biol., 2015, 6, 454–460. Q1

Energetic characterization of the system (water + 1-propoxypropan-2-ol) at T= 298.15 KM. L. C.J. Moita, M. C. Reis, A. F.S. Santos, Isabel M.S. LampreiaJ. Chem. Thermodyn. 2015, 91, 172-176. IF: 2.423 Q1

Alkaline hydrolysis of tertiary N-(2-pyridyl)carbamates. Contradictory evidence between nucleophilic and general base catalysisD. Silva, F. Norberto, S. Santos, P. HervésReact Kinet Mech Cat 2015, 115, 421–430. IF: 1.17 Q3

Hyperthermia studies of ferrite nanoparticles synthesized in the presence of cottonS.G. Mendo, A.F. Alves, L. P. Ferreira, M. M. Cruz, M. H. Mendonça, M. Godinho and M. Deus CarvalhoNew J. Chem. 2015, 397, 182 – 7193. IF:3.086 Q1

Validation of the Steinrath Index Predictions for the Degree of Soil Aggressiveness Toward Copper Corrosion in Soils Contaminated with ChloridesI.T.E. Fonseca, E. Niculita, I. Ornelas, M.D. Carvalho, and P.D. Vaz. Corrosion 2015, 71, 1267-1277. IF: 0.925 Q2

Development of tertiary thioamide derivatives to recover palladium(II) from simulated complex chloride solutionsO. Ortet, A.P. PaivaHydrometallurgy, 2015, 151, 33–51. IF: 1.933, Q1

New Strategy to prevent adhesion of Biofouling to CoatingsE. R. Silva, O. Ferreira, J. C.M. Bordado, J. Adhesion Society of Japan, 2015, 51, 239-240. IF: 1.417

Friction reduction on recent non-releasing biocidal coatings by a newly designed friction test rigA.V. Tulcidas, R.Bayon, A. Igartua, J. M.Bordado, S. M. Olsen, E. R. Silva, Tribol Int, 2015, 91 140-150. IF: 1.936 Q1

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Stir-bar Sorptive Extraction: 15 years making sample preparation more environment-friendlyJ.M.F. NogueiraTrends Anal Chem, 2015, 71, 214-223. F:6.472 Q1

Unravelling the antioxidant potential and the phenolic composition of different anatomical organs of the marine halophyte Limonium algarvenseM.J. Rodrigues, A. Soszynski, A. Martins, A.P. Rauter, N.R. Neng, J.M.F. Nogueira, J. Varela, L. Barreira, L. Custódio. Ind. Crop. Prod., 2015, 77, 315–322. IF: 2.837 Q1

Application of Bar Adsorptive Microextraction-Large-Volume Injection-Gas Chromatography-Mass Spectrometric Method for the Determination of Trace Levels of Agrochemicals in Real Matrices J.R. Bernarda, S.M. Ahmad, C. Almeida, N.R. Neng, J.M.F. NogueiraJ. Braz. Chem. Soc., 2015, 00(00), 1-9. F: 1.13 Q2

Biological Activities and Chemical Composition of MethanolicExtracts of Selected Autochthonous Microalgae Strains from the Red SeaH. Pereira, L. Custódio, M.J. Rodrigues, C.B. de Sousa, M. Oliveira, L. Barreira, N.R. Neng, J.M.F. Nogueira, S.A. Alrokayan, F. Mouffouk, K.M. Abu-Salah, R. Ben-Hamadou, J. Varela.Mar Drugs, 2015, 13(6), 3531-3549. IF: 2.853 Q2

Determination of mitragynine in urine matrices by bar adsorptive microextractionN.R. Neng, S.M. Ahmad, H. Gaspar, J.M.F. NogueiraTalanta, 2015, 144, 105-109. IF: 3.545 Q1

Determination of Steroid Sex Hormones in Real Matrices by Bar Adsorptive Microextraction (BAμE)C. Almeida, J.M.F. NogueiraTalanta, 2015, 136, 145-154. IF: 3.545 Q1

Synthesis of titanate nanofibers co-sensitized with ZnS and Bi2S3 nanocrystallites and their application on pollutants removal T.J. Entradas, J.F. Cabrita, B. Barrocas, M.R. Nunes, A.J. Silvestre, O.C. MonteiroMater Res Bull, 2015, 72, 20-28. IF: 2.288 Q2

Recovery of palladium(II) from a spent automobile catalyst leaching solution A.P. Paiva, G.I. Carvalho, M.C. Costa, A.M.R. Costa, C.A. NogueiraProceedings of WASTES: Solutions, Treatments and Opportunities – 3rd International Conference (Eds. C. Vilarinho, F. Castro, J. Carvalho, M. Russo, J. Araújo) pp. 61-63, Ed. CVR – Centro para a Valorização de Resíduos, Viana do Castelo, Portugal, September2015 (Proceedings).

Biomembrane Organization and Function: The Decisive Role of Ordered Lipid Domains J. T. Marquês, C. A. C. Antunes, F. C. Santos, R. F. M. de Almeida In A. Iglic, C. Kulkarni, M. Rappolt, eds.: Advances in Planar Lipid Bilayers and Liposomes, Vol 22, ADPLAN, UK: Academic Press, 2015, pp 65-96

Glycal Transformation into 2-Deoxy GlycosidesC. Dias, A. Martins, M. S. Santos, A. P. Rauter, M. Malik, In Carbohydrate Chemistry, Proven Synthetic Methods, Vol. 3, Ed. René Roy, Sébastien Vidal, pp.57-72, CRC Press 2015,ISBN: 978-1-4665-8357-3; eBook ISBN: 978-1-4665-8358-0 (book chapter)

Hierarchical Zeolites: Preparation, Properties and Catalytic ApplicationsA. P. Carvalho, N. Nunes, A. Martins in “Comprehensive Guide for Mesoporous Materials, Vol. 3: Properties and Development”, Ed. Mahmood Aliofkhazraei, pp. 147-211, Nova Science Publishers, Inc. 2015, ISBN: 978-1-63463-318-5 (book chapter)

Potencial of Mentha pulegium for mosquito controlD. Rocha, M. Novo, O. Matos, A. C. Figueiredo, M. Delgado, M. D. Cabral, M. Liberato, C. MoiteiroRevista de Ciências Agrárias, 2015, 38, 157-167

Zeólitos hierárquicos: de curiosidade laboratorial à próxima geração de catalisadores industriaisA. Martins, N. Nunes, A.P. CarvalhoIngenium, 2015, Maio/Junho, 90-93

Liquid-Liquid Extraction of Palladium(II) from Chloride Media by N,N’–Dimethyl-N,N’-DicyclohexylthiodiglycolamideO. Ortet, A.P. PaivaSeparation and Purification Technology, October 2015 (accepted)

Environmental application of Ti/TiO2 anodes prepared by DC-magnetron sputtering: degradation of acid orange 7S. Sério, L.C. Silva, M. E. Melo Jorge, S.Ferreira, L.Ciríaco, M. J. Pacheco, A.LopesEnvironmental Engineering and Management Journal (accepted)

Anchoring of gold nanoparticles on graphene oxide and noncovalent interactions with porphyrinoidsS. M. Andrade, C. J. Bueno-Alejo, V. V. Serra, J. M.M. Rodrigues, M. G.P.M.S. Neves, A. S. Viana, S. M.B. Costa,ChemNanoMat, (accepted)

Complex internal rearrangement processes triggered by electron transfer to acetic acidP. Limão-Vieira, G. Meneses, T. Cunha, A. Gil, M.J. Calhorda, G.Garcia, F. Ferreira da SilvaJournal of Physics: Conference Series (accepted)

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FTICR-MS

Stopped-Flow with absorption and fluorescence detection

Multimode Atomic Force Microscope

Imaging Ellipsometer

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Equipment

FTIR

Steady-state and time-resolved spectrofluorimeter with polarization modes and double grating monochromators

Scanning Electrochemical Microscopy

NMR spectrometer*

*DQB equipment

87

Equipment

Probe Beam Deflection

Electrochemical Quartz Crystal Microbalance

Conventional Ellipsometer

Photocurrent Spectroscopy

Contact AngleGoniometer

88

Surface Plasmon Resonance

CQB 2015

We thank Fundação para a Ciência e Tecnologiafor funding UID/MULTI/00612/2013

Booklet data collection & organization

CQB Executive Committees 2012-2013 and 2014-2015

Rodrigo F. M. de AlmeidaMaria José Calhorda

Manuel E. M. PiedadeCarla D. Nunes

Amélia P. RauterMaria da Soledade Santos

M. Luísa SerralheiroMarta Silva

Ana S. Viana

Ana Mourato, PhD, Science manager