cyril ruckebusch lasir cnrs université lille nord de france

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Cyril Ruckebusch LASIR CNRS Université Lille Nord de France ITMO, SAINT PETERSBURG 17-12-2013

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Page 1: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

ITMO, SAINT PETERSBURG 17-12-2013

Page 2: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France
Page 3: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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…

Page 5: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 6: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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)

Page 7: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

7

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

Page 8: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

8

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

Page 9: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 10: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 11: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

Polytech-Lille Academic programs

Page 12: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 13: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

LASIR UMR CNRS LILLE1 Laboratoire de spectrochimie infrarouge et Raman

Page 14: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

- 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

Page 15: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

- 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

Page 16: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 17: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

ULTRAFAST TIME-RESOLVED SPECTROCOPY APPLICATION TO THE STUDY OF PHOTOFUNCTIONAL SYSTEMS

Page 18: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

- 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).

Page 19: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 20: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

(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

Page 21: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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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

Page 22: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

ELECTRON PARAMAGNETIC RESONANCE APPLICATION TO CHARGE SEPARATION IN MICRO-POROUS MATERIALS

Page 23: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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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Magnetic field (Gauss)

EP

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Spin carrier location

Unpaired elctrons

Fantom of carbonate rocks: layers of diamagnetic SiO2 and paramagnetic carbons

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Page 24: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

.

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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(Electron/hole pair)

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

Page 25: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

RAMAN SCATTERING, IR, UV-VIS… APPLICATION TO THE CARACTERISATION OF SINGLE PARTICLES, DUSTS, POLLENS, … AND THE IMPACT OF POLLUANTS IN NATURAL MEDIA

Page 26: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 27: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

IR FACILITIES

Spectrometer MAGNA 860 Nicolet

Diffuse reflexion cell ATR Diamant

Spectrometer Vertex70 Bruker

Page 28: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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)

in solid in liquidin liquidns(NO3

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90 µm

NH4NO3 RH 80%

76 µm

NH4NO3 particule RH 20%

Accoustic levitation environmental cell for Raman microscopy

Page 29: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

CHEMOMETRICS AND COMPUTATION AND CHEMISTRY SEVERAL EXAMPLES…

Page 30: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 31: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 32: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 33: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 34: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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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

Page 35: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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affected by optical diffraction

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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Dark pxl

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Methods: PALM, STORM

http://www.stanford.edu/group/moerner/

Page 36: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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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Page 37: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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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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Page 38: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

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

Page 39: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

- 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

Page 40: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France

Thank you for your attention

Page 41: Cyril Ruckebusch LASIR CNRS Université Lille Nord de France