Sylvie Marguet

Sylvie Marguet
French National Centre for Scientific Research | CNRS · CEA Saclay, IRAMIS, NIMBE UMR 3685

About

69
Publications
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Introduction
Sylvie Marguet received a Ph.D. in 1992 from Paris-XI University and a CNRS research position in 1993. After 20 years of research in the field of photo-induced processes in molecular systems, she has developped over the last decade a know-how in the synthesis of high quality Gold NPs for plasmonics, plasmon-driven-chemistry and medicine. These Gold nanohybrids are studied in collaboration with teams of experts to discover unexpected properties.

Publications

Publications (69)
Article
Full-text available
The integration of nano-emitters into plasmonic devices with spatial control and nanometer precision has become a great challenge. In this paper, we report on the use of a smart polymer to selectively immobilize nano-emitters on specific preselected sites of gold nanocubes (GNCs). The cunning use of the polymer is twofold. First, it records both th...
Article
Gold nanoparticles can produce reactive oxygen species (ROS) under the action of ultrashort pulsed light. While beneficial for photodynamic therapy, this phenomenon is prohibitive for other biomedical applications such as imaging, photo-thermal drug release, or targeted gene delivery. Here, ROS are produced in water by irradiating gold nanorods and...
Preprint
Full-text available
We propose a versatile, user-friendly approach, named (Computing Debye's scattering formula for Extraordinary Formfactors) (CDEF), to approximately calculate scattering profiles of arbitrarily shaped nanoparticles for small-angle X-ray scattering (SAXS) using Debye's scattering formula. This equation generally allows to compute the scattering patte...
Article
Singlet Oxygen Sensor Green (SOSG) is the most widely used fluorescent probe for detecting singlet oxygen (¹O2). ¹O2 can be efficiently produced by exciting the surface plasmon of gold nanoparticles with laser pulses. However, gold nanoparticles are usually embedded in a chemical stabilizer that can interact with SOSG, leading to erroneous detectio...
Article
Full-text available
Hybrid plasmonic nano-emitters based on the combination of quantum dot emitters (QD) and plasmonic nanoantennas open up new perspectives in the control of light. However, precise positioning of any active medium at the nanoscale constitutes a challenge. Here, we report on the optimal overlap of antenna’s near-field and active medium whose spatial d...
Article
Surface plasmon resonance can be used to manipulate light at the nanoscale. It was used here to trigger photopolymerization of an atom transfer radical polymerization (ATRP) molecular system, leading to a thin polymer shell at the surface of the metal nanostructure. The polymerization can be reactivated from the first polymer shell to covalently gr...
Article
A novel technique for the investigation of the radiative contribution to the electromagnetic local density of states is presented. The inelastic tunneling current from a scanning tunneling microscope (STM) is used to locally and electrically excite the plasmonic modes of a triangular gold platelet. The radiative decay of these modes is detected thr...
Article
A simple hand calculation method based on group theory is proposed to predict the near field maps of finite metallic nanoparticles (MNP) of canonical geometries: prism, cube, hexagon, disk, sphere, etc. corresponding to low order localized surface plasmon resonance excitations. In this article, we report the principles of the group theory approach...
Article
Full-text available
We evaluate experimentally and theoretically the role of the residual ligands and ambient environment refractive index in the optical response of a single spherical gold nanoparticle on a substrate and demonstrate the changes in the near- and far-field properties of its hybridized modes in the presence of the cetyltrimethylammonium bromide (CTAB) l...
Preprint
Full-text available
The two-photon luminescence (TPL) of gold nanoparticles (NP) was shown to result from the excitation of hot carriers, the plasmonic NP resonances playing an important role both for plasmon enhanced absorption and plasmon enhanced emission. However, the exact parameters enabling to control or optimize the NP nonlinear luminescence still need to be u...
Article
Towards Accurate Analysis of Particle Size Distribution for Non-Spherically Shaped Nanoparticles as Quality Control Materials - Volume 25 Supplement - Ulrich Mansfeld, Francesco Pellegrino, Valter Maurino, Sylvie Marguet, Fabienne Testard, Olivier Tache, Vasile-Dan Hodoroaba
Article
The two-photon luminescence (TPL) turn-off in small single gold nanorods (GNR) exposed at increased resonant femtosecond laser excitation (800 nm wavelength, pulse energy density varying from 125 µJ.cm⁻² to 2.5 mJ.cm⁻²) is investigated. The origin is shown to be a photo-induced decrease of the rod aspect ratio. Such aspect ratio reduction could rea...
Article
A simple group theory approach is proposed to predict the charge distribution of low order localized surface plasmon resonances (LSPRs) of finite metallic particles of basic geometries. As an illustration, the case of randomly oriented Au colloidal particles of cubic C4v symmetry excited at dipolar resonance is presented. The symmetry approach is c...
Article
Full-text available
Homodimers of noble metal nanocubes form model plasmonic systems where the localized plasmon resonances sustained by each particle not only hybridize but also coexist with excitations of a different nature: surface plasmon polaritons confined within the Fabry-Perot cavity delimited by facing cube surfaces (i.e. gap plasmons). Destructive interferen...
Article
The two-photon luminescence (TPL) of small 10 nm x 40 nm colloidal gold nanorods (GNR) is investigated at the single object level, combining polarization resolved TPL and simultaneously acquired topography. A very high dependence of the TPL signal intensity with both the nanorods longitudinal axis and the incident wavelength is observed confirming...
Article
The inelastic tunnel current in the junction formed between the tip of a scanning tunneling microscope (STM) and the sample can electrically generate optical signals. This phenomenon is potentially of great importance for nano-optoelectronic devices. In practice, however, the properties of the emitted light are difficult to control because of the s...
Conference Paper
The origin of the two-photon luminescence in colloidal gold nanorods, investigated at the single level, is discussed: we show the existence of a specific volume maximizing the two-photon luminescence intensity.
Conference Paper
The plasmonic properties of individual gold nanowires (NW) have been investigated using both two-photon luminescence (2PL) coupled to atomic force microscopy (AFM) and photoemission electron microscopy (PEEM) associated to low-energy electron microscopy (LEEM) measurements. Using these complementary near-field characterization techniques, comparati...
Article
We report on the angular distribution, polarization and spectrum of the light emitted from an electrically controlled nanoscale light source. This nanosource of light arises from the local, low-energy, electrical excitation of localized surface plasmons (LSP) on individual gold nanoparticles using a scanning tunneling microscope (STM). The gold nan...
Article
Full-text available
We imaged and quantitatively characterized electromagnetic hot spots near the surfaces of plasmon resonant gold nanocubes. The strongest fields are localized at the nanocube corners as Compared to those on the sides. The near field enhancement on the surface of the cube was imaged as a function of incident polarization, leading to information on th...
Article
We studied the near-field optical properties of colloidal gold nanocubes (GNCs) using a photochemical imaging method. This method is based on the vectorial molecular displacements, of photosensitive azo-dyes, which are sensitive to the polarization of the optical near-field of the GNCs. We analyzed the spatial confinement of both electromagnetic ho...
Article
Hybrid systems coupling gold nanoparticles to fluorophores have been realized, aiming to investigate the conditions to get two-photon fluorescence (TPF) enhancement effects through nanoantenna or Purcell effects. The use of gold nanorods (NR) was chosen : due to their anisotropic form they indeed exhibit two localized surface plasmon resonance (SPR...
Article
We report a near-field imaging study of colloidal gold nanocubes. This is accomplished through a photochemical imaging method in which molecular displacements are vectorial in nature, enabling sensitivity to the polarization of the optical near-field of the nanocubes. We analyze the confinement of both electromagnetic hot and "cold" spots with a re...
Article
Titania nanoparticles are widely studied for photoconversion processes where combining high surface area, charge transport properties, and chemical stability is meaningful. To enhance the conversion efficiency, new compounds with reduced band gap are actively researched to utilize the visible part of the solar spectrum. Some narrowing of the gap ca...
Article
In the bottom-up approach of nanoscience and nanotechnology, nanoparticles are the first step towards nanostructured materials. The laser pyrolysis (LP) method appears as a versatile method for synthesis of various oxide and non-oxide nanoparticles. The method is based on the interaction of a powerful IR laser beam with a mixture of gaseous or liqu...
Article
UV radiation is well known to provoke skin cancers by triggering photochemical reactions potentially leading to an alteration of the genetic material. DNA damage may be << direct >> if photons are absorbed by the DNA helix, or << indirect >> if photons are absorbed by other molecules present within the cell. Pyrimidine (thymine, cytosine) dimers an...
Article
Il est bien connu que le rayonnement UV provoque des cancers de la peau. Cela se produit parce que des réactions chimiques, susceptibles d'altérer l'information génétique, se déclenchent sous l'effet de l'énergie apportée par la lumière. Les photons absorbés par l'ADN donnent lieu à des dommages « directs » tandis que les photons absorbés par d'aut...
Article
The investigation of model DNA helices using time-resolved absorption and fluorescence spectroscopy with UVB/UVC excitation knows currently an increasing interest due, in particular, to the use of femtosecond spectroscopy. The study of such complex and fragile systems presents specific difficulties which are not encountered in the experiments perfo...
Article
The ionization of the DNA single and double helices (dA)20, (dT)20, (dAdT)10(dAdT)10 and (dA)20(dT)20, induced by nanosecond pulses at 266 nm, is studied by time-resolved absorption spectroscopy. The variation of the hydrated electron concentration with the absorbed laser intensity shows that, in addition to two-photon ionization, one-photon ioniza...
Article
Full-text available
Absorption of ultraviolet light by DNA is known to lead to carcinogenic mutations, but the processes between photon absorption and the photochemical reactions are poorly understood. In their study of the excited-stated dynamics of model DNA helices using femtosecond transient absorption spectroscopy, Crespo-Hernández et al. observe that the picosec...
Article
The formation of thymine dimers in the single-stranded oligonucleotide, (dT)20, is studied at room temperature by laser flash photolysis using 266 nm excitation. It is shown that the (6-4) adduct is formed within 4 ms via a reactive intermediate. The formation of cyclobutane dimers is faster than 200 ns. The overall quantum yield for the (6-4) form...
Chapter
UV exposure of DNA is known to trigger off photochemical reactions that ultimately may lead to carcinogenic mutations. However, the primary UV-induced processes in DNA preceding such reactivity remain unclear even after several decades of intense studies. With this in mind, we have recently undertaken a program aiming at improving the understanding...
Article
Cytosine methylation, which determines the hot spots for DNA photo-damage, is shown to induce a red-shift of the nucleoside absorption spectrum, making the chromophore more vulnerable to solar radiation, and a tenfold increase of the fluorescence lifetime, making excited statereactions more probable. A femtosecond investigation of the excited state...
Article
Fluorescence anisotropy decays of the 7-diethylamino-4-methylcoumarin C1 in various polar solvents of different viscosities and hydrogen bond donor/acceptor character have been recorded by means of the fluorescence upconversion and time-correlated single photon counting techniques. The resulting characteristic times for the rotational diffusion fal...
Article
The room temperature fluorescence properties of DNA nucleoside and nucleotide aqueous solutions are studied by steady-state and time-resolved spectroscopy. The steady-state fluorescence spectra, although peaking in the near UV region, are very broad, extending over the whole visible domain. Quantum yields are found to be mostly higher and the fluor...
Article
The emission and excitation spectra of four phenylated [70] fullerenes, C70Ph4, C70Ph6, C70Ph8, and C70Ph10 in cyclohexane and toluene solutions have been measured. The fluorescence spectra and related excited state properties are found to depend strongly on the number of attached phenyl groups, but with no systematic trends. Quantum yields and flu...
Article
Triplet excitation transport occurring in the columnar liquid crystalline phase of a triphenylene derivative at room temperature is studied by transient absorption spectroscopy with nanosecond resolution. The properties of the triplet excitons are evidenced by doping the mesophase with different concentrations of 2,4,6-trinitrofluoren-9-one (TNF) w...
Article
Electronic coupling is the driving force for energy transfer in molecular materials and consists of several components. We determine the strength of dipolar/multipolar coupling and coupling due to orbital overlap for excitation transport in triphenylene columnar liquid crystals. We use time-resolved fluorescence spectroscopy and computer simulation...
Article
A new fluoroionophore bearing two crown ethers on the conjugated system, 1,5-bis[4N-(aza-15-crown-5)-phenyl]-1,4-pentadien-3-one (II), was synthesized together with model compound I where the crown ethers are replaced by diethylamino groups. The behavior of molecules I and II in the presence of alkali and alkaline-earth perchlorates was investigate...
Article
The spectroscopic properties of discotic hexa-alkylthiotriphenylenes are studied in solution and thin films and compared to those of hexa-alkyloxytriphenylenes. The solution properties are analyzed in the light of CS-INDO-CIPSI quantum chemistry calculations. The absorption maximum is assigned to the degenerate S0 → S4 transition. The fluorescence...
Article
The relaxation dynamics of charge carriers in 4 nm CdS colloidal quantum dots are studied by means of picosecond time-resolved fluorescence and femtosecond transient absorption experiments. We also studied the effects of the adsorption of viologen derivatives as electron acceptors on the surface of these particles. From these experimental measureme...
Article
Triarylpyrylium cations bearing an electron donating group are studied in solution by two pump-probe techniques with picosecond and nanosecond resolution. The transient spectra recorded on the picosecond time-scale as a function of solvent viscosity are in agreement with the formation of a TICT (twisted intramolecular charge transfer) state, predic...
Article
The photophysical properties of three discogenic dibenzopyrenes substituted by eight pentyloxy (O5DPB), heptyloxy (O7DBPP) or decyloxy (O10DBP) side chains are studied in solution and thin films. It is shown that the absorption and fluorescence spectra of the columnar mesophases are clearly distinguishable from those of the corresponding crystallin...
Article
The spectroscopic properties of two phenylethynylbenzene derivatives capable of forming nematic discotic (N D ) liquid crystals are studied in solution and in their N D phase. Their electronic absorption spectra are analysed with the help of fluorescence anisotropy measurements and on the basis of a previous theoretical study. The results presented...
Article
The singlet electronic states of hexaphenylethynylbenzene derivatives are calculated combining S-CI calculations in the π system and CS-INDO-CIPSI calculations in the σ and π systems (conformations spectra-intermediate neglect of differential overlap-configuration interaction by perturbative selected iterations). S-CI calculations (singly configura...
Article
Full-text available
Laser flash photolysis (at 248 or 308 nm) or aryl iodides in water or water/methanol solutions produces iodine atoms and phenyl radicals. Iodine atoms react rapidly with added I− to form I2− but do not react rapidly with O2 (k ⩽ 107 L mol−1 s−1). Iodine atoms oxidize phenols to phenoxyl radicals, with rate constants that vary from 1.6 × 107 L mol−1...
Article
The reaction of phenyl radicals with oxygen, to produce phenylperoxyl radicals, and the reactions of several phenylperoxyl radicals with a number of organic compounds in aqueous solutions have been studied by pulse radiolysis. Phenyl radicals were produced by reduction of aryl halides with hydrated electrons. The rate constant for the reaction of 4...
Article
Absolute rate constants for one-electron oxidation of free base porphyrins (hematoporphyrin-IX, mesoporphyrin-IX dimethyl ester) by the trichloromethylperoxyl radical and by the radical cation of N-methylindole have been determined in a variety of solvents by the pulse radiolysis technique. All solvents were air-saturated and contained CCl[sub 4] a...
Article
A new chemical actinometer is presented with improved sensitivity, precision and reproducibility with respect to potassium ferrioxalate. Based on the analytical measurement of the cis-isomer formation of a widely used styrenic laser dye, 4-dicyanomethylene-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran (DCM) upon photoexcitation, this actinometer is...
Article
Pinacyanol chloride (PC) is a better saturable absorber than DODCI in hybridly mode-locked Rhodamine 6G and Rhodamine B dye lasers, due to its higher chem. and photochem. stability. Using PC, stable femtosecond laser pulses can be generated for months without changing the saturable absorber soln. PC also allows a more efficient suppression of satel...
Article
The solvent-induced changes of trans-cis isomerization efficiency and electronic structure of the excited state of the DCM dye have been considered by means of CS INDO MRCI calculations. The potential energy curves, dipole moments and atomic charge densities as a function of two internal coordinates, namely the rotation angle about the central “dou...
Thesis
Cette étude du colorant laser styrénique 4-(dicyanométhylène)-2-methyl-6-[p- (diméthylamino) styryl]-4H-pyrane ou DCM nous a permis de caractériser la nature des premiers états électroniques et l'influence du solvant sur les efficacités des différents processus de relaxation du premier état excite S1 du DCM. Le DCM qui possède un groupe donneur d’é...

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Projects (2)
Project
At nanometer scale, the metallic particles exhibit new optical properties related to the plasmon resonance phenomenon. This effect holds great promise for a large range of applications ranging from information technology to renewable energies and biomedicine. A plasmon resonance is a collective and coherent oscillation of the conduction electrons at a metallic nanoparticle surface under the influence of an external electromagnetic field. The resonance wavelength depends on the nanoparticle characteristics, the external environment and the illumination geometry. My research project aims to implement these plasmonic properties for the manipulation of light at small scale and thus allow the emergence of innovative technologies. To do this, the optical response of various metallic nano-objects of different geometries and sizes, taken individually: cube, prism ... or in groups: dimer, chain ... are studied by PhotoEmission Electron Microscopy (PEEM), a non-intrusive and high resolution (10 nm) mapping technique allowing a selective addressing of plasmons modes. In addition to this experimental investigation, the search for a specific optical near-field distribution is also carried out using group theory, an original theoretical method allowing to predict the results in just a few minutes.