Cyril Ruckebusch LASIR CNRS Université Lille Nord de France
ITMO, SAINT PETERSBURG 17-12-2013
1.1 M. people
4th french urban area, rank 15 in Europe
28% below 20
100 000 students
80 M. people in a radius of 300 km
Lille is 1h to Paris 30 min to Brussels 1h20 to London
15 head office of major companies : Decathlon, Leroy Merlin, Auchan, Redcats, Lesaffre, Arc, Roquette…
The University of Lille 1- Teaching
Louis PASTEUR (1854-1914)
The University of Lille 1- Teaching
20 000 students
2000 enrolled in the Institute of Technology (I.U.T.)
9000 enrolled in bachelor’s degree programs
6500 enrolled in master’s degree programs
1500 enrolled in engineering
1000 enrolled in doctoral programs (The largest French university for doctoral students, with a growing number of co-supervised dissertations:143 out of 1000)
1 400 professors, assistant-professors and researchers
1 200 administrative staff members
3 Academic Divisions
Science and Technology (IT, maths, physics, chemistry, biotechnology, nanotechnology, mechanical engineering, civil engineering…)
Economics and Management (Economics, international economics, marketing, management science, human resource administration, logistics, bank and financial management)
Social Sciences (Education sciences, sociology, geography, urban planning
The University of Lille 1- Research
39 research laboratories
Mixed units with public research organizations: CNRS, INRA, INSERM, etc.
Lille 1 is the leader for 2 “Labex” (Laboratories of Excellence)
- CaPPA / Air Environment Physics and Chemistry
- CEMPI / European Centre for Mathematics, Physics and their interaction
Lille 1 is a partner in 3 “Labex”
- DISTALZ / Innovative strategy development for an interdisciplinary approach to Alzheimer's disease
- GANEX / GaN National Network –
- ICST / Ion Channels of Therapeutic Interest
Lille 1 is heavily involved in 2 Institutes of Excell.
and 1 Institute of Technological Research
- IFMAS / French Institute for Agro-Sourced Materials
- PIVERT / Plant innovation
- RAILENIUM / Rail infrastructure innovation
A success story: VAL Entirely automatic urban rail
(Pr Gabillard 1983)
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The University of Lille 1- An international institution
4661 foreign students
15.8% in Bachelor’s
31.1% in Master’s
55.3% in PhD programmes
16 degree programs taught entirely in English
10% of students undertake an outgoing mobility
Lille1 holds the 3rd place in national Erasmus rankings
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Strategy in 3 areas
Be the go-to French partner of universities in North-Western Europe
Reinforce ties with Japan, Canada and the United States
Develop strategic alliances with universities in a number of countries outside of Europe: Morocco,
Algeria, Lebanon, China, Vietnam, Indonesia, Brazil, Argentina, Kazakhstan and Russia.
Erasmus Mundus Programmes
Member of 14 consortia (Central Asia, Latin America, Eastern Europe, Africa… etc)
Development of Double Diplomas (20)
Maintain our attractiveness while reinforcing outgoing mobilities for our students
The University of Lille 1- An international strategy
Agreements with ITMO, the University of Voronej, the University of
Belgorod, the Technical University of Voronej, the Technical
University of Belgorod
Cooperation with the Chambers of Commerce
Participation in the French-Siberian network (CNRS/Academy of
Science)
Joint-degrees with the University of Novossibirsk and the University
of Ekaterinburg.
The cooperation with Russia
Focus: Polytech-Lille
A graduate engineering school of the university of Lille1
Authorised by the "Commission des Titres d'Ingénieurs" (CTI) - Ministry of Higher
Education and Research
Polytech'Lille is a member of the French "Conférence des Grandes Écoles“
350 graduate students per year Master’s degree in engineering
100% of the student undergoing mobility
7 Academic programs
Multidisciplinary programs in the main scientific and technological fields
Polytech-Lille Academic programs
Eiffel scholarship a program from the french foreign affairs to
attract elite foreign students in Masters, Engineering and PhD
programs (founding from 12 to 36 months)
Outgoing Mobility:
Student Internships in research laboratories: up to 4 months
Semester study during Master2
Polytech-Lille Cooperation opportunities
LASIR UMR CNRS LILLE1 Laboratoire de spectrochimie infrarouge et Raman
- A joint research unit of the CNRS and Lille 1 University (UMR 8516): 80 % fundamental research vs 20 % applied - Linked to the Institute of Chemistry and secondarily to the Institute of Ecology and Environment of the CNRS - Member of the Chevreul Research Federation (FR 2638) – Lille1 “Chemistry and Materials” - 70 staff members: 45 permanent and 25 temporary - Visiting Prof. : H. Miasaka (Osaka), J. Hofkens (Leuven), D. Kirsanov (St Petersburg) in 2013
LASIR OVERVIEW
- Main research domains: Physical Chemistry - Molecular spectroscopy applied to the study of complex systems - LASIR initial expertise in the field of vibrational spectroscopies (Raman scattering, infrared absorption) Invention of the Raman microprobe (Delhay and Dhamelincourt in 1975)
- Today the scope of expertise of the Laboratory has expanded considerably…
LASIR OVERVIEW
Scientific expertise
• Molecular spectroscopy (Vibrational, UV-Vis, lumines., NMR, EPR…) • Raman micro-imaging, IR et RPE • Near-field optics, AFM • Ultrafast transient absorption spectroscopy • Computational chemistry, Chemometrics • Spectroscopic Instrumentation and methodological development
Advanced instrumentation operated by ingenieers
• Center for microspectrometry and Raman microimaging multi-excitation from UV to IR • Center for spectrometry and microspectrometry NIR and mid-IR • National CNRS center for spectrometry and imaging EPR continuous and pulsed • Center for ultrafast spectroscopy (Abs UV-Vis, fluorescence, IR et Raman...)
Applications fields
• Environmental issues: aerosol, heavy metals complexation • Photoreactivity • Materials (polymer, glasses, pigments…) • Supercritical fluids • Catalysis • Biochemistry • Cultural heritage
LASIR OVERVIEW
ULTRAFAST TIME-RESOLVED SPECTROCOPY APPLICATION TO THE STUDY OF PHOTOFUNCTIONAL SYSTEMS
- Transient Raman ps, ns
- Transient UV-vis absorption fs, ns
- Transient IR fs
- Time-resolved fluorescence fs-ps
CENTER FOR ULTRAFAST SPECTROSCOPY
Transient optical spectroscopy dedicated to the investigation of photophysical processes and photochemical reactivity in condensed phase.
Various types of electronic and vibrational transient spectroscopic setups based on the use of the so-called “pump-probe” method and equipped with a choice of pulsed laser sources (femtosecond,
picosecond and nanosecond) covering a wide spectral range (UV to IR).
Transient states
CARACTERISATION OF THE EXCITED STATE DYNAMICS
From the understanding of elementary photochemical processes to the optimization and functionalization of complex photoactive molecular systems
(PHOTO-)FUNCTIONAL MOLECULES
. -> Evolution of the molecular dipole moments and fractions of charge transfer between groups
Photophysics of the intramolecular charge transfer of pyridinium betaines – Ligth activated molecules with application in photonics and non-linear optics
Phys. Chem. Chem. Phys., 2012, 14, 1945–1956
Transient absoption spectra and schematic of the photoinduced reaction after excitation
.
Photochromic behavior of salicylidene aniline confined in a self-assembled molecular capsule - Development of organic photoactive single molecule probes
(PHOTO-)FUNCTIONAL MOLECULES
ChemPhysChem 2011, 12, 1669 – 1672
Encapsulation: limited steric constraints of the host on the guest to act selectively on the ultrafast reactions of the guest: -> stabilizing the slowly decaying species, -> prohibiting the volume-demanding molecular twisting.
Transient absoption spectra, structure of Me2SA and schematic of the competitive photinduced reactions
ELECTRON PARAMAGNETIC RESONANCE APPLICATION TO CHARGE SEPARATION IN MICRO-POROUS MATERIALS
EPR CW
Pulsed EPR -ENDOR -ELDOR
Imaging EPR -Nuclear -Pulsed (2014)
EPR FACILITIES A national CNRS facility for EPR which provides information about the structural environment of unpaired electrons in materials
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Unpaired elctrons
Fantom of carbonate rocks: layers of diamagnetic SiO2 and paramagnetic carbons
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Zeolites porous structure enable to incorporate molecular species in a confined reaction space optimizing the charge-separation-state lifetime- Applications in photovoltaic conversion
PHOTO-INDUCED CHARGE SEPARATION WITHIN MICROPOROUS MAT.
Stable interfacial charge separation states upon intrazeolite adsorption of polyaromatic molecules -> Strongly absorbing in the visible
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Diffuse reflectance UV-vis and Pulsed EPR HYSCORE experiments after 2 months (electron/hole pair)
Valorisation of the charge separated state
Intrazeolite charge transfer process of trans-stilbene inserted within Na6,6ZSM-5. Non direct recombination and formation of a long lasting positive hole
RAMAN SCATTERING, IR, UV-VIS… APPLICATION TO THE CARACTERISATION OF SINGLE PARTICLES, DUSTS, POLLENS, … AND THE IMPACT OF POLLUANTS IN NATURAL MEDIA
LABRAM HR (473, 532, 633 nm) HoloLab 5000 Kaiser (785 nm)
LABRAM Vis. (514,5 et 633 nm) LABRAM HR UV (266 et 325 nm)
RAMAN IMAGING FACILITIES
IR FACILITIES
Spectrometer MAGNA 860 Nicolet
Diffuse reflexion cell ATR Diamant
Spectrometer Vertex70 Bruker
SPECTROCHEMISTRY OF COMPLEX SYSTEMS
Better understanding of the properties and photoreactivity of polluants (metals) in natural media
-> Combining in situ observations with model systems to chacterize single particles (size, morphology, phase, hygroscopic properties)
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Accoustic levitation environmental cell for Raman microscopy
CHEMOMETRICS AND COMPUTATION AND CHEMISTRY SEVERAL EXAMPLES…
CHEMOMETRICS
-Chemometrics for the resolution of process spectroscopy data (reactions, images, evolving chemical systems) -Resolution of unknown spectroscopic mixtures (TRS, EPR, Raman imaging, …) -Mechanistic information (rate constants, yield, …) -Spectral features
-Multivariate Calibration models for qualitative and quantitative prediction of properties of complex samples -Industrial collaborations (Total, Michemin, Roche, IFPEN, etc.)
-Statistical methods and data processing -Signal artifacts in ultrafast time resolution -Single-molecule and superresolution microscopy
Composition of textile products in NIRS
Contribution
pure #1
Contribution
pure #2
Contribution
pure #3
Super-resolution
5 mm
Superresolution IR imaging of a single HeLa cell
DECIPHERING THE EQUILIBRIA OF FIREFLY OXYLUCIFERIN A relatively simple molecule yet a quite complex chemistry
- OxyLH2: the fluorophore responsible of light flashes emitted by fireflies - A triple keto-enol equilibrium of 6 chemical forms at relevant physiological pH - Derivatives of firefly oxyluciferin were synthetized and analyzed in UV-
vis
To distangle the information (pH profiles and spectra) of the individual forms of oxyluciferin
M. Rebarz et al, Chem. Sci. 4 (2013) 3803
The MCR model: a low rank bilinear model that holds for multiset data arrangements
Column-wise matrix augmentation The MCR problem (MCR-ALS, ICA, PMF, BSS, …)
DECIPHERING THE EQUILIBRIA OF FIREFLY OXYLUCIFERIN
DECIPHERING THE EQUILIBRIA OF FIREFLY OXYLUCIFERIN Chemically oriented Multiset MCR-ALS
-> Pure spectra and pH-dependent profiles of OxyLH2
-> Reliable estimates of the equilibrium constants
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RESOLUTION OF OVERLAPPING SOURCES
LOCALIZATION OF SINGLE-MOLECULES
to unravel nm-details of molecular structures
DATATSUNAMI
NEW METHODS
inLive cells
Nano-CatalysisBiochemical processes
StatisticsPenalized regression
Multimodal pdfs
ChemometricsSource separation
Mixture resolution
©LASIR Univ-lille1
SINGLE-MOLECULE FLUORESCENCE IMAGING Resolution and localization of single-molecule fluorophores to unravel molecular structures in cell microscopy
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DECONVOLUTION OF SINGLE-MOLECULE FLUORESCENCE IMAGING DATA
Functional super-resolution microscopy using stochastic optical fluorescence single molecules probes (quantum dots, photoactive proteins, …)
Resolution enhancement breaking the diffraction the limit : --> Deconvolution --> Localization, PSF
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http://www.stanford.edu/group/moerner/
DECONVOLUTION OF SINGLE-MOLECULE FLUORESCENCE IMAGING DATA
Sparse spike deconvolution handling the convolution model in a penalized least-squares framework (Background, Blind deconvolution, Localization)
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A smooth background modelled by tensors of P-
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Sparse spiky signals estimated by penalized regression with a penalty based on L0-norm (the sum of non zero-elements)
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DECONVOLUTION OF SINGLE-MOLECULE FLUORESCENCE IMAGING DATA
Sparse spike deconvolution
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PALM (PhotoActivation Localization Microscopy) superesolution image of actin filaments (<10nm) labelled with a photoconvertible fluorescent protein probe in cells. Conventional image (left) processed (right)
Conventional and processed image of live HEK293 cells expressing a construct encoding the fluorescent protein Dronpa targeted to the plasma membrane. Samples were excited using a 488 nm laser line and 2000 images were acquired in rapid succession, using 10 ms exposure time per image.
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DENSITY EVALUATION IN SUPERCRITICAL FLUIDS Small changes in (P, T) conditions result in large changes in density, allowing fine tuning of physico-chemical properties providing economical and ecological benefits
- Combining molecular dynamics simulation and data clustering - Characterising local density inhomogeneity distribution in SCF
J. Phys. Chem. B 2013, 117, 12184−12188
Temperature dependence of the Ar−Ar radial distribution functions and density domain of Ar
system
-> Assesing the inhomogeneity of density domain distributions of Ar system in sub- and supercritical conditions (generalization to molecules…)
DBSCAN algorithm (Density Based Spatial Clustering of Application with Noise) for
non-linear separation
- CNRS GDRInternational PHENICS “PHoto-switchableE orgaNIC
molecular systems & deviceS” since 2008 - O. Fedorova, Department of Chemistry, Moscow State University - A. V. Metelitsa, V. I. Minkin, Southern Federal University, Rostov-on-Don
- Marie Curie Program (International Research Staff Exchange Scheme)
- M. Kiselev , Institute of Solution Chemistry of the Russian Academy of Science, Ivanovo
- One-to-one collaboration - M. B. Smirnov, Physics institute, University of St. Petersburg Spectral
features of phase transitions in oxydes - D. Kirsanov, ITMO, St Petersburg, Process Spectroscopy Chemometrics
RESEARCH COLLABORATIONS
Thank you for your attention
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