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Center for Structural Chemistry (Global Report for 2011 Activity)
The Center for Structural Chemistry (CQE) is organized in seven groups of research.
Each group develops several lines of research but in many cases there are collaborations
between one or more of them due to the interdisciplinary character of many of the
subjects undertaken.
The total number of members of CQE consisted in 2011 of 103 PhD and ca. 27
collaborators and several other research students who were supported by grants, from
FCT and others Institutions. CQE also received several temporary guest investigators
from an Erasmus program, bilateral collaborations or Networks involving members of
CQE. There were also collaborators from other national or foreign Institutions having
part of their activities in CQE.
CQE also disposes of a Technical Staff and an Administrative Staff.
CQE has an organizational structure with an administrative staff and multi-personal
boards to supervise and direct execution of the program which guarantee the general
functioning of the scientific and administrative aspects. The specific scientific matters are
left to each group leader who directs autonomously the research within the group. One
should note that the limited administrative staff puts an unnecessary administrative
burden to the researchers involved.
The funding of CQE was mainly given through FCT, involving the Strategic Programme
or specific national or international projects involving members of CQE. Of this funding,
ca. 16.7 % is an Overhead which is given to Instituto Superior Técnico. Private
companies or other international agencies have also provided funding through specific
services during 2011. While funding received from industries much higher than that
received in 2010 the amount received from Projects and FCT significantly decreased.
Although the general objectives of the CQE cover a broad area from experimental to
theoretical Chemistry, the activities are focused towards the two-fold task of teaching and
research nature of the Department of Chemistry and Biological Chemistry at IST. The
main aim of CQE is the training and qualification of young researchers who join it.
The CQE disposes of an infrastructure which is well equipped and renewed through 3
National Re-equipment Projects and participation in 2 National Networks of NMR and of
Mass Spectrometry. The quality of the available laboratories and the safety conditions
are not always in line with the minimum standards required for this kind of research.
The most significant areas at the CQE are: Inorganic/Organometallic/Organic Chemistry,
Bioinorganic Chemistry, Catalysis, Molecular Thermodynamics, Photochemistry and
Environmental Chemistry. A variety of techniques have been developed to over the
research in these areas: spectroscopic, electrochemical, crystallographic, potentiometric
and chromatographic techniques.
The main themes within Bioinorganic Chemistry, in 2011, have been the interplay of
Chemical Elements in Biology, the interaction of relevant biological ligands with metal
ions and prospective therapeutic applications of coordination compounds.
CQE was also increasing its involvement in developing systems using metal ions for
activation of small molecules, as well as homogeneous and heterogeneous catalysts for
the synthesis of compounds of pharmaceutical and/or industrial relevance.
The Coordination/Organometallic Chemistry research had covered Synthesis, namely by
chemical and electrochemical methods and mechanistic studies encompassing catalytic
systems, Thermochemistry, Mass Spectrometry, Crystallography. The supramolecular
synthesis and physicochemical studies on pharmaceutical compounds and BioMOFs;
computational studies on structure and reactivity; reactions energetic and NMR/SSNMR
studies on Biological systems and Biomaterials are the most new and challenging topics.
The Organic Chemistry is particularly focused to synthetic and mechanistic issues in
organic, bioorganic and bioorganometallic chemistry, major interests being therapeutic
and toxicological properties of bio-active compounds, synthesis and assessment of
organic molecular conductors, and mechanistic aspects of intramolecular charge transfer
reactions.
Research activities in the area of Molecular Thermodynamics include: Molecular
Modeling, Equations of State and Phase Equilibria, Thermophysical Properties of Fluids,
Physical Chemistry of Surfaces and Interfaces, Supercritical Extraction, micronization
and Thermodynamics of Materials/Biomaterials. Novel and promising systems and
technologies with applications in the areas of environment and biomedicine are being
developed.
The studies in Photochemistry deal with the Chemistry of Excited States, directed to
mechanisms of electron and proton transfer processes in molecules and supramolecular
systems. Absorption, fluorescence and laser flash photolysis are the most used
spectroscopic/kinetic methods. Recently also research on photonics and plasmonics
became more important.
Research is also carried out in Environmental Chemistry of Natural Systems focusing on
chemical processes of trace metals in natural waters, aquatic bio-organisms, soils and
plants, to evaluate their bioavailability, mobility, fate and biological effects;
electrochemistry of metalloproteins and analytical methods for speciation purposes
Several activities were carried out towards the promotion of chemistry to Society and to
link University to Society. Namely several initiatives of “Education in Chemistry” at the
Secondary level, and local organizations are also carried out, involving both direct
contact in schools, exhibitions, development of didactic products, chemshows, TV
programs and e-learning tools.
A significant number of CQE researchers participated actively in Open Lab and
Chemistry Olympics initiatives. International Year of the Chemistry was also an
opportunity to approach Chemistry to the society
The research activity in 2011 resulted in 200 ISI publications, 8 patents and 103
conference communications. Although from a quantitative point of view the output is
very good to excellent some groups should be more ambitious considering the levels of
journals chosen. In 2011 13 Msc and 10 PhD theses were completed.
Reports of each group are included here.
Group I Bioinorganic Chemistry (2011)
1) Research Themes and Achievements
The research is organized along six lines:
a) Medicinal Chemistry
This research line goes from Chelating therapy protocols, Diagnosis and therapy,
Metalloenzymes inhibitors, Dual drug/synergistic effects, Delay/prevention of brain
disorders, Bioavailability of drugs, to Anticancer, antiparasitic and insulin mimetic metal
complexes.
b) Drug design
Molecular toxicity, Bioavailability of drugs, Computational Chemistry and Molecular
Modeling.
c) Biological Chemistry
Studies with amavadine and cytochrome P450 models of industrial interest. Role of the
metal ions in biological evolution and in the human central nervous system. Selective
occurrence of D-amino acids in living organisms. Protein-drugs and DNA-drugs
interactions.
d) Reactivity in ionic liquids
Metal ion speciation and chemical reactivity of transition metal complexes in ionic
liquids. Development of systems for the desulfurization of diesel oils.
e) Catalysis
Homogeneous and heterogeneous catalysts, asymmetric synthesis, Catalysis in ionic
liquids, heterogeneization of catalysis, reaction mechanisms.
f) Environmental Chemistry
Sorption of metal ions by biomass rich in carbohydrates, cellulose fibers and by chelating
silica/resins. Analysis of trace organic compounds in drinking water and pharmaceutics.
Although, the lines are not developed at the same level and the distribution of researchers
is not homogeneous, good results were achieved in all of them as it can be checked in the
publications.
2) Equipment
The group is equipped with the experimental techniques necessary for the different
research lines: optical spectroscopies (UV-Vis, Fluorescence, Circular Dichroism, FT-IR),
Nuclear Magnetic Resonance, EPR, HPLC, HPLC-Ms, GC, GC-Ms, Potentiometry,
Molecular modeling, Viscosimetry, Electrophoresis. It has access to X-Ray
diffractometer, AFM microscopy at other groups of CQE and at other external national or
international groups which are collaborating.
3) Output, Visibility and Internationalization
The number of research papers published in 2011 was 28 with an average impact factor
of 4.101. The group has a great number of national or international collaborations
including other groups inside the CQE. Some of the research topics of this group overlap
with those of other groups and the collaboration between them is well justified. Two PhD
Thesis were defended in this year 2011, low in comparison with the high activity of the
group, while the number of M.Sc Thesis was 6. This fact reflects the strong restriction in
the possibility to contract young researchers. The group has incorporated new foreign
post-doc. The number of national or foreign PhD students is also low in comparison with
that of other groups. Some of the students are from Universidade de Algarve, who are
involved in one of the research line of the group.
4) Organization and sustainibility
The group consists of 9 senior researchers (permanent staff and assistant researcher), and
13 more junior researchers (junior postdocs, PhD students and research fellows). One of
the main limitations of this group is, however, the quality and surface of laboratories and
rooms for students. This problem is extensible to other groups of CQE but in this case is
more visible. The group received funding from FCT Base (Plurianual Program) and
through 2 research Projects. The total amount is clearly low to finance the research
undertaken by the group. Some problems related to the lack of funding to maintenance of
the equipment and the lack of technicians were not yet solved; the number of
administrative persons is not sufficient to support the bureaucracy of each group as a
consequence senior researchers employ many of their time in administrative subjects that
can be handled by administrative staff, in detriment of the research.
Group II Organometallic Chemistry and Homogeneous Catalysis (2011)
1) Research Themes and Achievements
The research is organized along seven lines:
a) Synthesis towards new catalytic systems and biological applications
This research line goes from studies on Ni(II) complexes as potential Al-free
polymerization catalysts to the synthesis of alpha- diimine Cu(I) complexes for catalytic
application in the cycloaddition of azides with alkynes, from the development of
heterogenization methods for single-site catalysts for application in homo and
copolymerization of olefins to synthesis of metal complexes with camphor-derived
ligands for application as catalysts in C-C or C-X (X=O, N, S) bond formation and uses
of organic camphor derivatives in tests for HIV-1 and HIV-2 transcriptases inhibition.
b) Synthesis of functional materials
New iminopyrrole based complexes for application in polymerisation catalysis and as
luminescent materials for the production of OLEDs; Fe(II) and Ru(II) organometallic
complexes for NLO materials; homo and heterobimetallic systems as molecular wires;
bioinspired Metal Organic Frameworks (BioMOFs)
c) Computational studies on reaction mechanisms
Computational (DFT) mechanistic studies on spin forbidden reactions; Molecular
modeling studies applicable in the design of zeolites
d) Supramolecular and solid state chemistry
New API solid forms (cocrystals and molecular salts) with enhanced pharmacological
properties,; polymorphism and cold crystallization in pharmaceutical compounds
Molecular mobility studies on species with pharmaceutical relevance.
e) NMR/SS-NMR studies on structural biology and on bio/materials.
Identification of metabolites in cell extracts of Saccharomyces; SS-NMR and Stray-Field
MRI studies of composite resins; Characterization of hydrophobic sol-gel materials
Elucidation of heterogeneous olefin epoxidation; decolorization of industrial azo and
anthraquinone dyes by a bacterial laccase.
f) Reaction energetics
Calorimetric studies on the energy-structure relationship of crystalline organic and
organometallic molecules with pharmacological activity.
g) Interaction with society and chemical education
Establishment of links between university and society; New didactic tools
Most of the seven lines were developed at a very good level: important and excellent
results were achieved in most of of them as it can be checked in the publications.
2) Equipment
The group is equipped with the experimental techniques required by the different
research lines: UV-Vis, Fluorescence, Circular dichroism, solution and solid state NMR,
EPR, FT-IR, HPLC, HPLC-MS, GC, GC-MS, DSC, TG, X-ray diffraction,
electrochemical techniques, Atomic Force Microscopy, Polarized Hot Stage Microscopy.
3) Output, Visibility and Internationalization
The number of research papers published in 2011 was 44, most of them in journal with an
ISI Impact Factor >3.0. The group has a great number of national or international
collaborations (> 20) including other groups inside the CQE. 2 patents, 3 books and 22
communications have been also produced by the group II members. Some of the research
topics of this group overlap with those of other groups and the collaboration between
them is well justified. Three PhD Thesis were defended in this year 2011. The group
productivity increases with the passing years, as also the reputation of the group members
and of the group leader as evidenced by the growing number of oral presentations at
meetings and conferences. A member of the group acts also as a chemistry expert
consultant for pharmaceutical industry.
4) Organization and sustainability
The group consists of 16 Faculty Staff (permanent staff and assistant researcher) and ca
10 junior researchers (junior post-doc PhD and MSc students and research fellows. The
group received funding from FCT Base (Plurianual Program) and through NMR Network.
The total amount allows financing the research undertaken by the group. One of the
major limitations is the number of administrative persons that is not sufficient to support
the bureaucracy of this group as also for the others. For this reason the senior researchers
employ a lot of time in administrative subjects in detriment of the research. The quality of
the available laboratories and the safety conditions are in line with the minimum
standards required for this kind of research.
Group III Molecular modeling and Photochemistry 2011
1) Research Themes and Achievements
The research is mainly organized along four lines
a) Thermophysical properties of fluids (including the supercritical state) of and
crystallization from supercritical fluids
This research line goes from the equations of state of binary liquid mixtures (over a large
temperature and pressure range and with e.g. a potential interest for coal liquidification)
to the use of supercritical phases to prepare nanocrystals, often of pharmaceutical
interesting molecules. The thermophysical characterization of liquids also involves
studies of the solubility of gases over a large temperature and pressure range or
determination of viscosity of highly viscous reference systems. The work with
supercritical CO2 led to supercritical antisolvent micronization of minocycline and fusidic
acid and fluid assisted micronization of lysozyme. Also cocrystallization was explored
Especially the research on the formation of nanocrystals and crystal engineering is very
novel and has a high potential for applications. As the group has very good possibilities
for modeling it would be interesting to apply them on the formation of nanocrystals and
the corresponding cocrystals to obtain predicting power on the effect of experimental
conditions on the lattice and habitus of the nanocrystals formed. Considering the
application potential collaboration with possible industrial partners, possibly in the
framework of an EU project should be sought actively. Also close interaction between the
different sections of the group working on this topic should be enhanced.
b) Ionic liquids
The bulk and surface properties of ionic liquids are addressed by various techniques and
linked with molecular modeling. This possibility to link experimental work with
modeling is a very strong point. This research is timely and of high level and should be
continued or expanded.
c) Nanostructured materials
The bulk and surface properties of fluorinated and semifluorinated alkanes (and mixtures
with other compounds) are studied by a combination of imaging and classical surface
chemistry techniques and the obtained results are linked to different types of computer
modeling. A second subtopic is related to the thermoresponsive behavior of
blockcpolymers where optical microscopy (in collaboration with CQFM) is combined
with AFM. Both topics are relevant considering the present interest in nanostructured and
self-organized systems. For the optical imaging of the surfaces collaboration with other
groups at CQE and CQFM should be enhanced. As the number of researchers involved in
this work is rather small the two subgroups should try to collaborate intensively with
other groups on (inter)national level. This will one hand give them access to experimental
techniques not available in the group and on the other hand allow them to identify timely
and relevant topics in this field.
d) Biomedical and pharmaceutical applications
This research line focuses on one hand on the tribology of prosthetic materials and on the
other hand to drug delivery. As this work is of less fundamental interest it is essential to
valorize it by collaboration with other institutes as well as companies working in the field.
In this way the relevance of the work will be granted in the long term. For the work on
biomembranes the existing collaboration with group IV and the CQFM should be
enhanced.
2) Equipment
The group is, equipped with a large number of experimental techniques necessary for the
different research lines. It has been able to acquire good quality commercial instruments
(AFM, LB troughs, viscosimeter, tensiometric instruments, microbalances, tribometers. It
has also an impressive potential to build its own instruments which is especially
important for the work on supercritical liquids and determination of thermophysical
properties at high pressure. A possible bottler neck can be the attraction of junior
researchers willing to work on instrumental development. It has further access to optical
microscopy, spectroscopic methods, X-Ray and electron microscopy either at other
groups of CQE or CQF and outside the chemistry institute of the technical university.
3) Output, Visibility and Internationalization
From a quantitative point of view the output of research papers is, considering the size of
the group very good and of the same level as the other groups of CQE (38 papers of
which 16 in high impact journals(IF > 3)). Although smaller than in 2010 the output
clearly increased compared to 2009; however the number of papers in a journal with IF >
3 continues to increase. There were 3 master theses and 1 PhD thesis which is of similar
level as in 2009 and 2010. Also two patents were obtained.
The documented number of contributions at international conferences is relatively low
(2), but is possible there were more contributions which did not result in a contribution to
the proceedings. The group should try to maintain or if possible increase the number of
oral presentations and invited lectures as this aspect of its visibility is beneficial for
further participation in European research networks.
The group has a very extensive set of local (inside IST), national and international
collaborations, mainly at a bilateral level. For this aspect it is clearly above the average
level of CQE. It should also participate in EU projects which is not only important from
the point of view of funding but also to stay connected with high level groups working on
the different topics investigated in group III. Considering the large spread in topics in
group III extensive collaboration (inside the technical university, on the national and
international level) remains essential to have a minimal critical mass involved in each
topic. This is necessary for efficient progress in and timely feed back on the different
topics.
4) Organization and sustainibility
The group consists of 10 senior researchers (permanent staff and assistant researcher) and
20 more junior researchers (junior postdocs, PhD students and research fellows). While
this 1/3 ratio is excellent for continuity and transfer of know-how, a larger number of
junior researchers would probably lead to a more efficient use of the experience of the
senior researchers. I would however note that the same problem exists at other groups at
CQE. The limited possibility to attract junior researchers is perhaps related to the
incorporation of the group (and the CQE) in a technical university where the interest of
students towards more specific fundamental chemical and biochemical problems is
limited. This could be solved by closer interaction with other Lisbon universities as the
good experimental facilities in the group can be expected to be attractive.
Besides the FCT base funding the group obtained funding from 7 national projects, some
of them with very substantial funding, which is sufficient considering its size. Also one
industrial project was obtained in 2011 which is important considering orientation of this
group versus applications. While the availability of government related financing is
probably very limited the investigation by the group of several topics with a high
application potential should enable it to attract European or further industrial funding.
The group should try to participate in EU funded networks which would allow to hire
more junior researchers and to intensify the collaboration with groups doing related
research or having complementary experience.
Group IV Photochemistry 2011
1) Research Themes and Achievements
The research is mainly organized along two lines
a) Photochemistry of supramolecular and nanostructured systems
In this line the group acquired a major experience in the use of photophyics to investigate
surfactant assemblies forming vesicles, nanospheres and inverse micelles and to study
photophysical properties of single molecules and plasmonic systems. This experience
was e.g. used to study the effect of plasmonic interactions on the photophysics of a
phthalocyanine incorporated in ionic self-assembled multilayers. The latter work as well
as the work on single molecule electron transfer and interaction between nanotubes or
graphene and porphyrins are a valuable and original contributions to emerging research
directions in photophysics and should be continued. Also the development of novel
porphyrin-rhodamine conjugates as bimodal probes is interesting from a fundamental
(charge transfer transition) as applied (bio-analytical) point of view. The kinetics of
aggregation and conformational changes in -lactoglobulin is investigated as model
system for prion forming proteins of medical importance.
Although the research is generally novel and timely the small number of researchers on
each topic requires that the group looks for active (inter)national cooperation in order to
be able to progress in those rapidly developing fields and have sufficient and timely feedback for their results and planning of new research.
b) Ultrafast kinetics
Besides the study of fundamental photophysical processes (especially excited state proton
transfer) in natural and synthetic chromophores also excited state relaxation and
thermochromism in conjugated polymers and oligomers model systems were proved. As
the latter systems are investigated intensively worldwide for potential applications in
organic light emitting diodes (OLEDs) and organic photovoltaic devices (OPVs) it is
strongly advised to continue this work.
As the number of researchers involved in this work is rather small the group should try to
collaborate intensively with other groups on (inter)national level. This will one hand lead
to access to ultrafast pump probe spectroscopy and on the other hand allow them to
continue to identify timely and relevant topics in this field.
The group also started to investigate the effect of vibronic states on electrocyclic ring
closure in photochromic systems. The theoretical work (in collaboration with other
groups) on the latter topic will be extended towards experiments. Here again extensive
(inter)national collaboration is advised to get access to experimental techniques not
available in the group and to be able to follow closely recent developments in this field.
c) Intramolecular electron transfer
One should also note the work of group VII on intramolecular electron transfer where the
combination of EPR and spectro-electrochemistry allows to determine the rate of this
proves and to elucidate the parameters influencing this rate. Depending on the type of
compound for molecules of similar distance between the radical anion centers either a
delocalized or localized state was formed. This work is much closer to work on photoinduced electron transfer in both research lines of group IV than to the work performed in
group VII and one should consider transferring the corresponding team to group IV.
2) Equipment
The group is, considering its size, well-equipped with different stationary and time
resolved techniques (single photon timing, fluorescence upconversion, confocal
microscopy, nanosecond flash photolysis, fluorescence lifetime imaging and fluorescence
correlation spectroscopy). Although the set-ups for single photon timing and confocal
microscopy are (due to financial limitations) not high end ones, the excellent skills,
experience and knowledge of the researchers allow them to get high quality experimental
data and to do sophisticated data interpretation (e.g. with global analysis). The set-ups are
used intensively and are in very good shape. For the confocal microscopy acquisition of a
CCD camera would allow to get (with a rather limited investment) besides images and
fluorescence decays also spectra of single molecules or single fluorescent objects. It
would be advantageous to acquire directly a nanosecond gated intensified CCD camera
which would allow them to use the camera also to upgrade the nanosecond flash
photolysis set-up. Such acquisition is strongly advised. For the study of fluorescence
decays and fluorescence microscopy a close coordination between the two research lines
in the group and between groups at CQFM using similar equipment would be advisable
in future to ensure optimal use of the financial resources.
Collaboration with other groups at the CQE (e.g. group III) allows them to get access to
other instrumentation (Langmuir Blodgett), to obtain interesting compounds (porphyrins
rhodamine conjugates, conjugated oligomers and polymers) and to have access to
quantum mechanical modeling. Acquisition of ultrafast pump probe spectroscopy would
be valuable for research topics in both research lines; however the running cost of such
equipment would probably be excessive considering the size of the group.
3) Output, Visibility and Internationalization
From a quantitative point of view the output of research papers is (10), considering the
size of the group very good and of the same level as the other groups of CQE. Part of the
work is published in excellent journals (PNAS!!, J Phys Chem. C, J Mater. Chem.).
Considering the fact some of the topics investigated are currently of great interest, the
group should try to publish larger part of its work in general chemistry journals as Journal
of the American Chemical Society or Chemistry a European Journal. The output is
smaller than in 2010 but at the level of 2009. In 2011 n PhD or master theses were
completed.
The group had 4 poster presentations, 1 oral communications and 1 invited lecture at
international conferences. The group should try to increase further this aspect of its
visibility which also will be beneficial for participation in European research networks.
The group has a very extensive set of local (inside IST), national and international
collaborations, mainly at a bilateral level. Considering its small size those collaborations
are essential for the viability of the group as well for obtaining access to novel tailor
made chromophores or chromophore assemblies and the access to experimental
techniques, as for the timely development of novel research themes.
4) Organization and sustainability
The group consists of 8 senior researchers (permanent staff and assistant researcher) and
8 more junior researchers (junior postdocs, PhD students and research fellows). While
this ½ ratio is excellent for continuity and transfer of know-how, a larger number of
junior researchers would probably lead to a more efficient use of the experience of the
senior researchers. I would however note that the same problem exists at other groups at
CQE. The limited possibility to attract junior researchers is perhaps related to the
incorporation of the group (and the CQE) in a technical university where the interest of
students towards more specific fundamental chemical and biochemical problems is
limited. This could be solved by closer interaction with other Lisbon universities as the
good experimental facilities in the group can be expected to be attractive.
Considering its size the group did very well the last years the last years in acquiring
research projects which are furthermore a from several different sources. In 2011 the
group obtained (besides the Base FCT funding) funding from 5 (national) projects. This
is comparable with the funding obtained by larger groups in the CQE program! Although
compared to 2010 the funding deceased it is still higher than in 2009. The group should
try to participate in EU funded networks which would allow to hire more junior
researchers and to intensify the collaboration with groups doing related research or
having complementary experience.
Group V Coordination Chemistry and Molecular Electrochemistry,
Synthesis and Catalysis (2011)
1) Research Themes and Achievements
The research is organized along seven lines:
a) Catalytic alkane functionalizations under mild conditions
Mild hydocarboxylation of alkanes to carboxylic acids; mild carboxylation and oxidation
of alkanes; kinetic and mechanistic studies of selected catalytic alkane reactions;
development of supported catalytic systems upon heterogeniz. of homog. catalysts.
b) Catalytic alcohols oxidations under mild conditions
New catalysts for selective aerobic oxidation of alcohols.
c) Catalytic C-C couplings
New metal catalysts for Suzuki-Miyaura cross-couplings; new stereoselective catalysts
for nitroaldol (Henry) C-C coupling.
d) Catalysis under unconventional conditions
Non-transition metal catalytic systems; metal-free and/or solvent-free systems;
microwave assisted green processes; supercritical fluid media.
e) Metal-mediated Syntheses
Direct template syntheses of triazapentadiene complexes from organonitriles; syntheses
of azoderivatives of beta-diketones (ABD) and their complexes; syntheses of Nheterocycles upon dipolar cycloadditions (CA) with nitriles or isocyanides; syntheses of
metal carbenes
f) Syntheses of Catalyst Precursors
New complexes bearing differenr chelating N- and/or O- and/or S- and/or P-ligands
g) Polynuclear and supramolecular metal structures
Self-assembly synthesis of homo- and heterometallic polynuclear and supramolecular
assemblies. Syntheses by metallaligands coordination.
h) Aqueous Organometallic/Coordination Chemistry
Complexes with functionalized hydrosoluble scorpionates or aminophosphine PTA
applications in crystal engineering, photoluminescence, catalysis.
i) Bioinorganic and biological Studies
Biomimetic catalytic systems; synthesis of cytotoxic metal complexes against human
cancer cell lines and of DNA interaction for selected compounds; identification of
biological targets; use of Zebrafish to identify novel drugs for hypertrophic
cardiomyopathy (HCM) therapy.
j) Electrochemical Studies
Investigation of complexes by CV and CPE
k) Theoretical Studies
Study of selected reactions, namely towards understanding properties of new complexes,
activation processes and establishment of reaction mechanisms.
Most of the 11 research lines were developed at an excellence level: important and
interesting results were achieved in most of of them as it can be checked in the
publications. The distribution of researchers is quite homogeneous.
2) Equipment
The group is equipped with the experimental techniques required for the different
research lines: High-Pressure reactors, Microwave reactor, supercritical fluid reactor,
ozonizer, thermogravimetric balance, NMR, EPR, FT-IR, Far FT-IR, HPLC, X-ray
diffraction, electrochemical high-vacuum/inert gas flow set-up, luminescence
spectrometer, UV-Vis, GC, GC-Ms.
3) Output, Visibility and Internationalization
The number of research papers published in 2011 was 53, most of them in journal with an
ISI Impact Factor >4.0. The group has a great number of national or international
collaborations (> 25) including other groups inside the CQE. 3 awarded patents, 4 invited
lectures, 20 international communications, 9 national communications have been also
produced by the group V members. Some of the research topics of this group overlap
with those of other groups and the collaboration between them is well justified. 1 PhD
Thesis and 4 MSc theses were defended in this year 2011. The group productivity
increases with the passing years, as also the reputation of the group members and of the
group leader as evidenced by the growing number of oral presentations at meetings and
conferences. The group leader is strongly active in the organization of conferences and
seminars. The group leader exhibits an excellent h-index (>40) and the research level is
very high with clear and of general interest objectives
4) Organization and sustainability
The group consists of 12 Faculty Staff (permanent staff and assistant researcher), 2
Invited scientists and ca 20 junior researchers (junior post-doc and PhD students and
research fellows. The group received funding from FCT Base (Plurianual Program) and
through Formation projects. The total amount allows financing the research undertaken
by the group. One of the major limitations is the number of administrative persons that is
not sufficient to support the bureaucracy of this group as also for the others. For this
reason the senior researchers employ a lot of time in administrative subjects in detriment
of the research. The quality of the available laboratories and the safety conditions are not
in line with the minimum standards required for this kind of research. Other important
limitation is the number of permanent members and the poor availability of X-ray
diffraction facilitites, as also the lack of SEM and TEM facilities.
Group VI Chemistry and Electrochemistry of Natural Systems 2011
1) Research Themes and Achievements
The research is mainly organized along two lines
a) a more fundamental line on the electrochemistry of metal containing proteins
In this line the group built up a major experience in the interfacing of different types of
metal proteins to electrodes and implemented several novel and sophisticated Volta
metric techniques. The group has also the necessary contacts to obtain the purified metal
proteins (cytochromes, peroxidases) sometimes containing uncommon (in biological
systems) transition metals as molybdenum or tungsten. Although the research is novel
and timely further extension of (inter)national cooperation with groups that are able to
further exploit the obtained results would give extra leverage to the achievements.
b) a more applied line on uptake and detoxification of metal containing contaminants by
aquatic organisms
In this research line the uptake of several toxic elements (either in solution or as
nanoparticles) by marine organisms as algae and mollusks is investigated. The research
involves the trajectory from harvesting of the organisms, uptake of the (toxic) substances
under well controlled conditions and determination of the concentration of those
substances in the organisms. Appropriate analytical techniques were developed and
special attention is paid to the speciation of the elements inside the organisms. The latter
question is e.g. of high importance to study the toxicity of nanoparticles. Also for this
research (inter)national collaborations grant that timely research topics will be
investigated
2) Equipment
The group is, considering its size, well-equipped with different (electro-)analytical
techniques and has sufficient facilities for the controlled growth and sampling of the
different organisms studied. Besides the instruments it is clearly able to use them in an
efficient way allowing adequate data acquisition and data interpretation. Furthermore It
has access to more complex analytical methods by (intern) national collaboration. It is (as
long as the group has the same size) probably not advisable to acquire the latter methods
as a too large fraction of the available manpower will be attributed to the set-up and
operation of those methodologies.
3) Output, Visibility and Internationalization
From a quantitative point of view the output of research papers (10) is, considering the
size of the group (see below) very good to excellent and at least of the same level as the
other groups of CQE. Furthermore the impact remains very good and now 5 out of 10
papers are in a journal with impact factor above 3 while the average impact has increased
from 2.1 in 2009 and 2.8 in 2010 to 2.9. Furthermore 1 PhD and 1 MSc thesis was
completed in the group in 2011. No oral presentations or invited lectures at international
conferences are indicated in its report. The group should try to increase this aspect of its
visibility which also will be beneficial for participation in European research networks.
The group has a very extensive set of local (inside IST), national and international
collaborations, mainly at a bilateral level. Considering its small size those collaborations
are essential for the viability of the group as well for obtaining access to the proteins
necessary for the electrochemical studies and to more sophisticated analytical techniques
as for the timely development of novel research themes.
4) Organization and sustainability
The group consists of 5 senior researchers permanent staff and assistant researcher) and
10 more junior researchers (junior postdocs, PhD students and research fellows). While
this ½ ratio is excellent for continuity and transfer of know-how, a larger number of
junior researchers would probably lead to a more efficient use of the experience of the
senior researchers. I would however note that the same problem exists at other groups at
CQE. The limited possibility to attract junior researchers is perhaps related to the
incorporat0on of the group (and the CQE) in a technical university where the interest of
students towards more specific fundamental chemical and biochemical problems is
limited. This could be solved by closer interaction with other Lisbon universities as the
good experimental facilities in the group can be expected to be attractive. The funding of
the group consists (besides FCT base funding) of 3 national projects. Compared to 2009
and 2010 the total funding has increased significantly. Considering size of the group the
funding is quite adequate. Considering the present financial situation in Portugal the
group should try to participate in EU funded networks. This would not only allow it to
hire more junior researchers but also to intensify the collaboration with groups doing
related research or having complementary experience.
Group VII Organic and Bioorganic Chemistry (2011)
The research is organized along seven lines:
a)
Drugs design Design, synthesis and evaluation of:
* Organic and organometallic selective estrogen receptor modulators (SERMs) as
potential anticancer agents
* Chalcogenated flavonoids as antioxidants, enzyme inhibitors and cell signaling
modulators.
b)
Molecular Toxicology
Studies of the long-term toxicity associated with chronic therapies and with exposure to
xenobiotics from dietary or environmental sources.
c)
High-valent Oxo Complexes and Catalysis
* High-valent oxo complexes as activators of X-H (X = Si, B, P) bonds and as
catalysts for organic reductions
* Carbohydrates as chiral scaffolds for the asymmetric synthesis of biologically
important molecules
d)
Mixed Valence Organic Radicals
* Studies on the coexistence of localized and delocalized radicals
* Structural effects on charge delocalization
e)
Industry Consulting and Cooperation
* Scientific advising in patent issues
* Scientific advising in R&D and P&D
f)
Organic Molecular Conductors
Aromatic dithiols as ligands in transition metal complexes used as electron
acceptors for the preparation of charge transfer salts in combination with good electron
donors. These new materials can have interesting properties for second order NLO
activity.
g)
Mass Spectrometry
* Gas-Phase Ion Chemistry (FTICR/MS)
* Studies in solution (ESI-QIT/MS)
* Natural products, degradation of natural dyes, drugs metabolites and adducts,
or synthetic dyes in historical stamps (LC-MS/MS)
* Terpenoid varnish resins (MALDI-TOF)
The group collaborates with other groups of the CQE, mainly with Group I and Group II and
uses a multidisciplinary approach to address synthetic and mechanistic aspects in Organic,
Bioorganic and Bioorganometallic Chemistry.
Equipment
The group is well equipped with the experimental techniques required for the different
research lines: optical spectroscopies (UV-Vis, Fluorescence, FT-IR), Resonance Raman
FTICR/MS, ESI-QIT/MS, Nuclear Magnetic Resonance, HPLC, HPLC-Ms, MALDI-TOFF,
X-Ray Diffraction, Electrochemical Techniques, Molecular modeling.
Output, Visibility and Internationalization
The number of research papers in peer review International Journal with IF >2.5 was 17,
and 1 more submitted what it corresponds to the same level as the other groups of CQE. 2
books and 1 book chapter were also published. The number of communications (posters and
oral presentations) at international conferences was quite good in 2011. The number of
presentations in national conferences was also noticeable. During 2011, 2 PhD theses were
defended 5 more are ongoing as well as 1 MSc thesis. The group increased its research
activity during 2011. Several projects of advanced training were also supervised by group’s
members. The group has very active international collaborations which cover the main
research lines. Active contacts with several industries partners have led to contracts. A patent
in the pharmaceutical field was also registered in 2011.
Organization and sustainibility
The group consists of 7 senior researchers (permanent staff and assistant researcher) and
more junior researchers (MSc students and research fellows). The number of researchers has
increased compared to the previous yers but it is low for big spread of the research lines. A
similar problem exists at some other groups at CQE. The limited possibility to attract junior
researchers is perhaps related to the incorporation of the group (and the CQE) in a technical
university where the interest of students towards more specific fundamental chemical and
biochemical problems is limited. This could be solved by closer interaction with other Lisbon
universities as the good experimental facilities in the group can be expected to be attractive.
The group received funding from FCT Base Programme, as well as through 4 research
Projects and 1 MSc Network. Funding from Industry was also obtained, and it corresponds to
a similar amount to that received from the FCT Base Programme. However, the total amount
is clearly low to finance the research undertaken by the group. The same problem that affects
to the other groups is the lack of funding to maintenance of the equipments and the lack of
technicians. Likewise, the number of administrative persons is not sufficient to support the
bureaucracy of each group and it reverts in detriment of the research since the senior
researchers employ many of their time in administrative tasks of which a large part could
easily be shifted to the administrative staff.