NEWS

NEW PROJECT APPROVED

A new LMCB international project has been approved, with classification of "Excellent",  by the Portuguese Science Foundation (FCT), with a total budget of 200.000,00 Euros.

"The Birth of Energetic Crystals from Isolated Molecules - The Unsuspected Parenthood of Rare Conformers"

Project

PTDC/QEQ-QFI/3284/2014 - (Prime Investigator: Rui Fausto)

SUMMARY: In general, molecular crystals are composed by molecules in one of their lower-energy conformations. The usual crystallization procedures (from melt, precipitation from solution, sublimation) are done in conditions where enough thermal energy is available to allow for conformational rearrangements to occur. Under these conditions, the less populated higher-energy conformers generally convert to the more populated lower-energy conformers, which become the constituting units of the crystals. Though more than one conformer might be present in a crystal, the most frequent situation is occurrence of conformational selection upon crystallization. In contrast, if a conformer is a high-energy form and is not populated at all (or is non-significantly populated) before crystallization, the probability of its selection is extremely small. For this to be possible, the packing forces must be strong enough to overcome the required very-unfavourable-energetically extensive conformational rearrangement. Imagine now that we can selectively generate a specific high-energy conformer of a molecule, from a dominant low-energy conformer, in a very efficient way and in such conditions that no thermal energy is available to allow its back-conversion to the most stable form, i.e., at very low temperature (a few K). Consider that we have also the possibility to do this for the isolated molecules, in a solid matrix of a frozen inert gas, so that no interactions between the molecules of the compound exist initially, and that we can subsequently evaporate the inert matrix and, in a controlled way, allow the molecules to diffuse to build progressively larger aggregates till production of a crystal, eventually of nanometric dimensions. If the condition of inexistence of enough thermal energy for conformational isomerisation is kept during this process (Ne evaporates below 20 K), the probability to produce a crystal composed by the high-energy conformer then becomes extremely high. Such crystal has a high-content of conformational energy, but the crystallization process is still energetically accessible because the precursor molecules have been prepared a priori in the proper high-energy conformation, while the aggregation processes (nucleation and growing) are energetically favourable steps. It is also conceivable that these crystals (an unsuspected parenthood of rare conformers) are stable enough to be warmed to temperatures high-enough to receive practical uses, in some cases to room temperature and above that. In this project, we will use as main tool to generate the high-energy rare conformers to engineer energetic-crystals the technique we have pioneered to selectively produce a specific conformer of a molecule using optical methods. This method consists in the use of narrowband selective Near-IR excitation of a high-frequency vibration of a precursor low-energy conformer isolated in a cryomatrix, followed by energy relaxation from the excited vibrational coordinate to the low-frequency torsion corresponding to the isomerization coordinate. Once the desired high-energy conformer is produced, the strategy described above will be followed to produce the novel energetic crystals. The probing and structural characterization of the different conformers (reactant and optically generated forms), their dimers and obtained crystals will be done by IR spectroscopy, which is extremely sensitive to structure changes and crystal packing. When crystals result to be enough stable at high temperature, they will also be characterized by other techniques (Raman, DSC, microscopy and X-ray).
Besides the leading edge conceptual nature of the project, the experimental procedures to be followed introduce also new approaches in use of innovative matrix-materials and development of a specialized set-up for synchronized irradiation and IR spectra collection. The project will also comprehend a strong state-of-the-art theoretical component. Besides up-to-date quantum chemical calculations on isolated molecules and dimers, models to identify the basic motifs present in the crystals, based on larger associates (up to 10 units), will be studied. The project will also take advantage of our recently developed method for calculation of anharmonic IR spectra, which will be extended to explicitly consider media. The research team has large experience in the domains of the project, molecular physics, matrix-isolation IR, and solid state and theoretical chemistry. It is an international team (8 nationalities represented), working on prestigious research units (U. Coimbra; S.N.S. Pisa; U. Helsinki), and puts together a partnership between Academy and a high-tech firm (Scarspec). The team is well-balanced in genders and experience, and the PI has verified competence in the management of very successful projects. Training is also an important output, with 3 PhD and 5 MSc theses being expected as result of this research.

Comments by the evaluation panel:

Criterion A - Scientific merit and innovative nature of the project from an international standpoint, including but not limited to: i) Relevance and originality of the project proposed (based on the state-of-the art in a determined scientific area and previous work done by the proposing team); ii) Methodology adopted for carrying out the project; iii) Expected results and their contribution to scientific and technological knowledge; iv) Resulting publications and articles; v) Contribution towards promoting and disseminating science and technology; vi) Production of knowledge that can be incorporated into and applied to the business sector.

Rating: Outstanding

Comments: This is a challenging risky project aiming at producing high-energy/unstable (rare) conformers from isolated stable molecules (by employing the cryospectroscopic techniques pioneered by the PI and his team) to be used for engineering energetic crystals, possibly stable enough for practical purposes and applications (namely, stable to warming at practically exploitable temperatures). The rationale is that by using optical methods it is possible to produce high energy conformers that, under cryogenic conditions, won't interconvert/ equilibrate and hence form crystals that would not form otherwise under equilibrium conditions. It is also argued that these crystals can be stable enough to be used in practical applications. This is of course questionable and should be proved, as the crystals created with this method will always be metastable and revert to the minimum free energy state, presumably in a short time, unless they are trapped rather in a glassy state. However, from the point of view of fundamental science, this is a really adventurous and interesting challenge that the PI and his consortium can take considering their quality (that stands at high international standards), both in terms of mastered state-of-the-art methodologies (spanning from experimental to computational techniques), characterization approaches, techniques/instrumentation development (e.g., the development of the para-H₂ production system, that also directly involve a company, Sarspec,: see task 2). 28 papers are expected. The training activity foreseen is also excellent (3 PhDs and 5 Masters). If successful, groundbreaking impact is expected both in terms of the general scientific knowledge in the field, techniques/instrumentation development (the Sarspec company is also involved) and applications related to stable crystals of packed high-energy conformers (e.g., exploitation for pharmacological purposes).

Criterion B - Scientific merit of the research team, including but not limited to: i) scientific productivity of the team (ranging from references to publications and citations in published works as used by the basic and engineering sciences, to performance and artistic work in the arts or monographs and books in the humanities and social sciences); ii) Abilities and skills to adequately execute the proposed project (team configuration, Principal Investigator's qualifications); iii) Ability to involve young researchers in training; iv) Availability of the team and non duplication of objectives in relation to other projects underway; v) The degree of internationalization of the team; vi) Degree of success in previous projects in relation to the Principal Investigator (PI).

Rating: Oustanding

Comments: : The PI is an outstanding scientist in the field targeted by the project, with an impressive record of publications on high impact international journal, excellent international reputation (including international project evaluation at the institutional level), outstanding granting score and PI activity (e.g, FCT granted projects), and excellent mentoring/training/supervision activity that can be also foreseen in the presented project (3 PhDs and 5 Masters have been scheduled). The consortium consists of 20 researchers, and is fairly international, with 8 different nationalities, and two foreign institutions, Pisa and Helsinki. The PI has allocated himself a significant amount of time for this project, showing his commitment. The consortium does also involve a high-tech firm that will be committed for the execution of task 2 (instruments development). The quality of the PI, the consortium and the wide-excellent cooperative network he can rely on, together with the record of previous results achieved, provide the most valuable insurance for a successful execution of the project. The abilities and skills needed to accomplish the project are all adequately contained in the consortium: some of the key methodologies exploited here to execute the tasks have been developed by the same PI and his team. Despite this proposal is on the mainstream of other funded projects and can be seen as an extension of them, non duplication of objectives in relation to them is clear as well as it is the novelty and the challenge related to engineering energetic-crystals and developing the techniques for doing that. Despite this is a very risky project, and its success rate is estimated to be low, the PI and his consortium can certainly take the challenge.

Criterion C - Feasibility of the plan of work and reasonableness of the budget, including but not limited to: i) organization of the project in terms of the proposed objectives and resources (duration, equipment, size of the team, institutional and management resources); ii) institutional resources of the participating entities, in particular of the Principal Contractor (PC) (technical-scientific, organizational and managerial and, when appropriate, co-funding capacity on the part of companies).

Rating: Outstanding

Comments: The project is very well structured, detailed and described, with clear goals and targets. Tasks (6 + 1 for management that is really essential for such a complex project) are also well illustrated and commented. Milestones description is also appropriate. The project is challenging and a risk analysis would be welcome. However, the high level of expertise of the PI and the consortium (including the involvement of a local high-tech company for instrumentation development: task 2), as well as the resources already available at the institutional level in terms of equipment and man power (the consortium involves 20 expert members) grants a high success rate, also considering the high success rate of previous projects coordinated by the same PI. The requested budget for the equipment (high resolution FTIR) is reasonable as it is an essential component for the execution of the project. The requested budget for human resources is limited (only 1 BPD), but may be still seen as adequate since the amount of human resources already available at the institutional level. The management of the project will take advantage of the supporting services available at the main institution, such as DAPI and DGF. The main institution also offers resources to facilitate patent preparation an submission. These have also been discussed in the project.

Criteria D and E - Contribution to the body of knowledge in this field and improvement of competence of the scientific community in general, including but not limited to: i) Contribution to the body of knowledge and competence of the National Science and Technology System (expected effects and results). Potential economic value of the technology (if appropriate), namely in terms of its impact on the competitiveness of the national socio-economic system.

Rating: Outstanding

Comments: The project would impact both on spectroscopic techniques as well as on some more basic science issues related to crystal engineering. More specifically, the project will provide information on how to generate rare conformers, which should be of interest to researchers working on chemical physics / physical chemistry, but also in pharmacological science (production of pharmacologically active solid phases). Some of the work will also be of interest in the area of low temperature physics, computational chemistry, and instrument development and molecular spectroscopy. The expected output on terms of 3 PhD and 5 MSc Theses is very good, and it contributes to the training of young scientist in an interesting area of researcher with practical applications in molecular spectroscopy. These students will also have the opportunity to interact with international leaders in the field, increasing their motivation and opening a number of professional career options to them.
This project, that also comprises a direct involvement of a high-tech company in task 2, is certainly expected to have a impact in instrumentation development, with possible applications and exploitable economical outcomes. Application of new engineered energetic-crystals is also expected to be very relevant in the future, e.g. medicinal and pharmacological sciences (production and delivery of pharmacologically active forms/states of drugs). However, as noted by the applicants, this is mainly a fundamental research project.

Overall Rating: Outstanding

Overall Comments: This is a challenging risky project aiming at producing high-energy/unstable (rare) conformers from isolated stable molecules (by employing the cryospectroscopic techniques pioneered by the PI and his team) to be used for engineering energetic crystals, possibly stable enough for practical purposes and applications (namely, stable to warming at practically exploitable temperatures). The rationale is that by using optical methods it is possible to produce high energy conformers that, under cryogenic conditions, won't interconvert/equilibrate and hence form crystals that would not form otherwise under equilibrium conditions. It is also argued that these crystals can be stable enough to be used in practical applications. This is of course questionable, as the crystals created with this method will always be metastable and revert to the minimum free energy state, presumably in a short time, unless they are trapped rather in a glassy state. However, from the point of view of fundamental science, this is a really adventurous and interesting challenge that the PI and his consortium can take considering their quality (that stands at high international standards), both in terms of mastered state-of-the-art methodologies (spanning from experimental to computational techniques), characterization approaches, techniques/instrumentation development (e.g., the development of the para-H2 production system, that also directly involve a company, Sarspec,: see task 2). The project is very well structured, detailed and described, with clear goals and targets. Tasks (6 + 1 for management) are also well illustrated and commented. Milestones description is also appropriate. The budget is appropriate for both equipment and human resources. 28 papers are expected. The training activity foreseen is also excellent (3 PhDs and 5 Masters). If successful, groundbreaking impact is expected both in terms of the general scientific knowledge in the field, techniques/instrumentation development (the Sarspec company is also involved) and applications related to stable crystals of packed high-energy conformers (e.g., production and delivery of pharmacologically active forms/states of drugs).

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NEW PROJECT SUBMITTED

A new project has been submitted to the "Fundação Calouste Gulbenkian", on the subject:

"Investigation of Museulogical and Archeological Objects by Raman Spectroscopy and Imaging".

This project will involve the LMCB and the Machado de Castro Museum (Prime Investigator: Bernardo Albuquerque).

LMCB INTEGRATES THE National Roadmap of Research Infrastructures of Strategic Relevance

The Portuguese Science Foundation (FCT) supports research infrastructures of strategic interest that sustain scientific and technological advancements and strengthen the scientific R&D&I community in Portugal, thus stimulating their active participation in European and international projects.
The LMCB, as a research unit of the LaserLab Coimbra infrastructure has been selected to integrate the National Roadmap of Research Infrastructures of Strategic Relevance integrated in the LASERLAB PORTUGAL research unit.

Painting by Agante (2008) showing the University and the Mondego banks, with the "Sanra Clara" bridge at the front!... Note the nice idea of the painter in making the sky replaced by a blackboard where we can see mathematical formulas. Coimbra fits well with knowledge!...

SEVEN YEARS AS MAIN EDITOR OF THE JOURNAL OF MOLECULAR STRUCTURE

RUI FAUSTO completed seven years as Editor-in-Chief of the prestigious Elsevier's international chemistry journal JOURNAL OF MOLECULAR STRUCTURE in February 2016. The team of main editors also integrates Profs. Austin Barnes (special issues and consulting editor), Jan Laane, Jan Lundell, Malgorzata Biczysko, Silvia Brandán and Elangannan Arunan.

The Journal of Molecular Structure is dedicated to the publication of full-length articles and review papers, providing important new structural information on all types of chemical species including:

• stable and unstable molecules in all types of environments (vapor, molecular beam, liquid, solution, liquid crystal, solid state, matrix-isolated,  etc.)

• chemical intermediates
• molecules in excited states
• biochemicals
• polymers.

The methods used may include any combination of spectros-copic and non-spectroscopic techniques, for example:

• infrared spectroscopy (mid, far, near)
• Raman spectroscopy and non-linear Raman methods
• force constant and molecular mechanics calculations
• electronic absorption spectroscopy
• optical rotatory dispersion and circular dichroism
• fluorescence and phosphorescence techniques
• electron spectroscopies (PES, XPS), EXAFS, etc.
• microwave spectroscopy
• electron diffraction
• NMR and ESR spectroscopies
• Mössbauer spectroscopy
• X-ray crystallography.

IMPACT FACTOR: 1.780

(Impact Factor in 2009: 1.486)
 

NIR induced conformational isomerization in hydroxyacetone

Electronic excitation is not the only way to picture photo-chemistry. Subtle transformations, not involving covalent bond breaking, can be brought about by selective excitation of a vibrational mode.

Hydroxyacetone, for instance, exists in two conformations differing only for a C-C bond rotation (see picture). Because of an intramolecular hydrogen bond, one of them, Cc, is more stable than the other, Tt, by 12 KJ mol^-1. Because of this, the Cc conformer represents 99% of all hydroxyacetone molecules at room temperature, so all photochemical studies of hydroxy-acetone have been, in effect, the study of its Cc conformer. However, there are theoretical hints that point towards a different photochemistry in terms of mechanism and rate constants between the two conformers.

In an elegant communication, Prof. R. Fausto and coworkers at the University of Coimbra (Portugal) reports the characterization of the elusive Tt conformer of hydroxyacetone in an Ar matrix at 15 K. The Cc → Tt transformation is induced by irradiation with infrared light at 6785 cm^-1, a frequency matching the first overtone (2ν) of the ν(OH) stretching mode, ν(OH), of Cc. Shift of the ν(OH) to higher frequency confirms the formation of Tt. Thermally stable at 15 K, Tt conformer generates back Cc by irradiating at Tt's 2ν(OH) (7138 cm^-1).

Significantly contributing to the expanding field of overtone-induced physical chemical transformations, this is an unusual example of infrared-induced single bond rotation involving spatial reorganization of a heavy atom, namely oxygen.

["Conformational Switching Induced by Near-Infrared Laser Irradiation", A.Sharma, I. Reva, R. Fausto, J. Am. Chem. Soc., 2009, 131, 8752-8753].

NEW RESEARCHERS JOIN THE LMCB

HAFSAE LAMSAF joined the LMCB team September 2016.

Hafsae Lamsaf is an Erasmus - Al Idrisi Ph.D. student from the University of Fez (Morocco). Her research project in Coimbra is centred in the structural and spectroscopic study of phosphates and phosphonates.

HALIMA HAZHAZI joins LMCB.

Halima Hazhazi is a Ph.D. student from the University Khider-Biskra (Algeria). Her research plan in the LMCB focus on the study of allenic tetrazoles and azides.

ANA PENEDA has been accepted as M.Sc. student at the LMCB.

Ana Peneda M.Sc. project, being developed in collaboration with the Machado de Castro Museum, is focused on the analysis of the Tresor of Queen Elisabeth and other jowels from the Museum by Raman spectroscopy.

RITA PIRES has been accepted as M.Sc. student at the LMCB.

Rita Pires M.Sc. project is developed in collaboration with the Laboratory of the Scientific Portuguese Police and centers on the analysis of paints used in printers.

ELISA BRÁS has been accepted as M.Sc. student at the LMCB.

Elisa Brás M.Sc. project deals with the study of heterocyclic compounds of nitrogen and sulphur by matrix isolation infrered spectroscopy, Raman spectroscopy and thermodynamic methods. The project involves also a strong theoretical component (using quantum chemical methods) and structural analysis by x-ray diffraction.

LMCB MEMBERS M.Sc. PUBLIC EXAMS

BERNARDO ALBUQUERQUE, passed his M.Sc. exam in October 2016.

Thesis: Structural and Spectroscopic Characterization of Hydantoins and Investigation of Their Thermal Properties and Photochemistry in Cryuogenic Matrices.

SANDRA PINTO, passed his M.Sc. exam in October 2016.

Thesis: Photochemistry of 1,2-Benzisoxazoles Isolated in Cryogenic Matrices: Identification and Structural Characterization of Reactive Intermediates.

ROCHA MANICO, passed his M.Sc. exam in February 2016.

Thesis: Raman Spectroscopy and Infrared Imaging in the Study of Fingerprints and Associated Explosives' Vestiges.

LMCB MEMBERS POST DOCTORAL GRANTS AWARDED

TIMUR NIKITIN, obtained a Post-Doctoral Grant, to continue his research at the LMCB. His work is centered on the preparation of high-energy crystals and runs within the scope of the Research Project "The Birth of Energetic Crystals from Isolated Molecules - The Unsuspected Parenthood of Rare Conformers".

LESZEK LAPINSKI, has been awarded a Post-Doctoral Grant for developing studies on the photochemistry of derivatives of cytosine and other heterocyclic compounds.

GULCE ILDIZ, has been awarded a Post-Doctoral Grant for developing studies on the spectroscopy and photochemistry of derivatives of hydantoin.

VISITS OF THE LMCB MEMBERS TO OTHER LABORATORIES WORLDWIDE

IGOR REVA, spent ca. 3 weeks at the Institute of Physics, Polish Academy of Sciences, Warsaw (Poland), September 2010, where he developed investigation using matrix isolation spectroscopy methods in the Laboratory of Prof. Maciej Nowak. The studies run under the ongoing collaborative work funded by Polish Science Foundation annd FCT (Portugal).

TIMUR NIKITIN, visited the Saint Petersburgh University (Russia), September 2016, to discuss the project of developing an experimental set up for spectroscopic studies of substances disolved in liquifed noble gases.

CLÁUDIO NUNES, spent ca. 1 month at the University of Wiscosin (USA), working under supervision of Prof. Robert McMahon on EPR and IR matrix isolation of nitrenes (2015).

LAST PAPERS ACCEPTED FOR PUBLICATION

Spectrochimica Acta A, 171 (2017) 207.
DOI: 10.1016/j.saa.2016.08.002

"Matrix Isolation Infrared Spectroscopic Study of 4-Pyridinecarboxaldehyde and of its UV-Induced Photo-chemistry."

L. CLUYTS, A. SHARMA, N. KUS, K. SCHOONE, R. FAUSTO
 

Journal of the American Chemical Society.
DOI: 10.1021/jacs.6b07368

"Evidence of a Nitrene Tunneling Reaction: Spontaneous Rearrangement of 2-Carboxyaldehyde Phenylnitrene to Imino Ketene in Low-Temperature Matrices."

C. NUNES, S. KNEZZ, I. REVA, R. FAUSTO, R. MCMAHON
 

Tetrahedron Letters, 57 (2016) 5038.
DOI: 10.1016/j.tetlet.2016.09.098

"On the Photochemistry of 3-Amino-1,2-Benzisoxazole: Unexpected Photoisomerization of a 2-Amino-Spiro-2H-Azirine to a 1H-Diazirine."

C. NUNES, S. PINTO, I. REVA, R. FAUSTO
 

RUI FAUSTO ELLECTED AS THE NEW EUCMOS PRESIDENT

RUI FAUSTO has been chosen as President of the International Steering Committee of the European Congress on Molecular Spectroscopy (EUCMOS), succeeding to Prof. Austin J. Barnes in this position. The EUCMOS series of meetings is among the most important ones at world scale, with the first congress of the series hold in 1947, immediatly after the II World War.
The next meeting of the series, EUCMOS XXXIV, will be held in Coimbra, August 19-24.

Promoting the LMCB