Exciton annihilation and diffusion length in disordered multichromophoric nanoparticles.

Efficient exciton transport is the essential property of natural and synthetic light-harvesting (LH) devices. Here we investigate exciton transport properties in LH organic polymer nanoparticles (ONPs) of 40 nm diameter. The ONPs are loaded with a rhodamine B dye derivative and bulky counterion, enabling dye loadings as high as 0.3 M, while preserving fluorescence quantum yields larger than 30%. We use time-resolved fluorescence spectroscopy to monitor exciton-exciton annihilation (EEA) kinetics within the ONPs dispersed in water. We demonstrate that unlike the common practice for photoluminescence investigations of EEA, the non-uniform intensity profile of the excitation light pulse must be taken into account to analyse reliably intensity-dependent population dynamics. Alternatively, a simple confocal detection scheme is demonstrated, which enables (i) retrieving the correct value for the bimolecular EEA rate which would otherwise be underestimated by a typical factor of three, and (ii) revealing minor EEA by-products otherwise unnoticed. Considering the ONPs as homogeneous rigid solutions of weakly interacting dyes, we postulate an incoherent exciton hoping mechanism to infer a diffusion constant exceeding 0.003 cm2 s-1 and a diffusion length as large as 70 nm. This work demonstrates the success of the present ONP design strategy at engineering efficient exciton transport in disordered multichromophoric systems.

Impact of 3D Curvature on the Polarization Orientation in Non-Ising Domain Walls.

Ferroelectric domain boundaries are quasi-two-dimensional functional interfaces with high prospects for nanoelectronic applications. Despite their reduced dimensionality, they can exhibit complex non-Ising polarization configurations and unexpected physical properties. Here, the impact of the three-dimensional (3D) curvature on the polarization profile of nominally uncharged 180° domain walls in LiNbO3 is studied using second-harmonic generation microscopy and 3D polarimetry analysis. Correlations between the domain-wall curvature and the variation of its internal polarization unfold in the form of modulations of the Néel-like character, which we attribute to the flexoelectric effect. While the Néel-like character originates mainly from the tilting of the domain wall, the internal polarization adjusts its orientation due to the synergetic upshot of dipolar and monopolar bound charges and their variation with the 3D curvature. Our results show that curved interfaces in solid crystals may offer a rich playground for tailoring nanoscale polar states.

Kinetics of protein-assisted nucleic acid interconversion monitored by transient time resolved fluorescence in microfluidic droplets.

Interconversions between nucleic acid structures play an important role in transcriptional and translational regulation and also in repair and recombination. These interconversions are frequently promoted by nucleic acid chaperone proteins. To monitor their kinetics, Förster resonance energy transfer (FRET) is widely exploited using ensemble fluorescence intensity measurements in pre-steady-state stopped-flow experiments. Such experiments only provide a weighted average of the emission of all species in solution and consume large quantities of materials. Herein, we lift these limitations by combining time-resolved fluorescence (TRF) with droplet microfluidics (DmF). We validate the innovative TRF-DmF approach by investigating the well characterized annealing of the HIV-1 (+)/(-) Primer Binding Sequences (PBS) promoted by a HIV-1 nucleocapsid peptide. Upon rapid mixing of the FRET-labelled (-)PBS with its complementary (+)PBS sequence inside microdroplets, the TRF-DmF set-up enables resolving the time evolution of sub-populations of reacting species and reveals an early intermediate with a ∼50 ps donor fluorescence lifetime never identified so far. TRF-DmF also favorably compares with single molecule experiments, as it offers an accurate control of concentrations with no upper limit, no need to graft one partner on a surface and no photobleaching issues.

Excited-State Proton Transfer in Oxyluciferin and Its Analogues.

One of the most characterized bioluminescent reactions involves the firefly luciferase that catalyzes the oxidation of the luciferin producing oxyluciferin in its first excited state. While relaxing to the ground state, oxyluciferin emits visible light with an emission maximum that can vary from green to red. Oxyluciferin exists under six different chemical forms resulting from a keto/enol tautomerization and the deprotonation of the phenol or enol moieties. The optical properties of each chemical form have been recently characterized by the investigations of a variety of oxyluciferin derivatives, indicating unresolved excited-state proton transfer (ESPT) reactions. In this work, femtosecond pump-probe spectroscopy and time-resolved fluorescence spectroscopy are used to investigate the picosecond kinetics of the ESPT reactions and demonstrate the excited state keto to enol conversion of oxyluciferin and its derivatives in aqueous buffer as a function of pH. A comprehensive photophysical scheme is provided describing the complex luminescence pathways of oxyluciferin in protic solution.

Broadband UV-Vis vibrational coherence spectrometer based on a hollow fiber compressor.

We describe a broadband transient absorption (TA) spectrometer devised to excite and probe, in the blue to UV range, vibrational coherence dynamics in organic molecules in condensed phase. A 800-nm Ti:Sa amplifier and a hollow fiber compressor are used to generate a 6-fs short pulse at 1 kHz. Broadband sum frequency generation with the fundamental pulse is implemented to produce a 400-nm, 8-fs Fourier limited short pulse. A UV-Vis white-light supercontinuum is implemented as a probe with intensity self-referencing to achieve a shot-noise-limited sensitivity. Rapid scanning of the pump-probe delay is shown very efficient in suppressing the noise resulting from low-frequency pump intensity fluctuations. Using either of the 800-nm or 400-nm broadband pulses as the pump for TA spectroscopy of organic molecules in solution, we resolve oscillatory signals down to the 320 nm probing wavelength with a 3200 cm-1 FWHM bandwidth. Their Fourier transformation reveals the corresponding molecular vibrational spectra. Finally, we demonstrate the use of this setup as a vibrational coherence spectrometer for the investigation of the vibrational dynamics accompanying the sub-ps C=C photoisomerization of a retinal-like molecular switch through a conical intersection.

Two MHz tunable non collinear optical parametric amplifiers with pulse durations down to 6 fs.

We report on the development of a 2 MHz non collinear optical parametric amplifier (NOPA) for high repetition rate time resolved X-ray or optical spectroscopy. Our modular and very flexible device is pumped by the second and third harmonics of a commercial femtosecond Ytterbium-doped fiber laser. The amplified pulses are tunable from 520 nm to 1000 nm with pulse durations between 15 and 30 fs over the full tuning range. The same setup is also suitable for broadband amplification and we demonstrate the generation of 6 fs pulses at a central wavelength of 850 nm as well as the generation of a broadband spectrum supporting 4.2 fs transform limited pulse duration at a central wavelength of 570 nm. Very high stability and compactness is achieved thanks to an optimized mechanical design.

Ultrafast site-specific fluorescence quenching of 2-aminopurine in a DNA hairpin studied by femtosecond down-conversion.

The ΔP(-)PBS analog of the DNA primary binding sequence (PBS) of the HIV-1 genome labeled at different positions by 2-aminopurine (2-AP) is investigated by a novel femtosecond fluorescence down-conversion experiment with 0.3-ps time resolution. The high signal-to-noise ratio of the fluorescence kinetics makes it possible to reveal four distinct decay times ranging from 0.8 ps to 2-3 ns for all the three labeling positions. This suggests the existence of at least four different quenching conformations of 2-AP with its nearest neighbors, and underscores the structural heterogeneity of the loop region of ΔP(-)PBS. Sub-5-ps components are found and attributed to stacking interactions of 2-AP with the flanking guanine (G) side chains, consistent with the NMR structure of ΔP(-)PBS. The observation of a significant increase of their total amplitude when 2-AP is positioned close to the rigid 3'-half of the G-rich stem gives further support to this assignment. Only a minor portion of conformations involves slow nanosecond collisional quenching.

Broadband transient dichroism spectroscopy in chiral molecules.

We perform time-resolved broadband transmission ellipsometry using the ultrafast pump-probe technique in an original setup. Our setup allows us to measure, over a wide spectral range, the optical rotary dispersion of the sample or, when needed, its circular dichroism by adding a broadband quarter-wave plate. While our experiment has been designed to study the transient states in chiral molecules, it performs sufficiently well to also characterize the ground state.

Photonic jet driven non-linear optics: example of two-photon fluorescence enhancement by dielectric microspheres.

The two-photon excited fluorescence from a dye solution is enhanced when a small amount of micro-meter sized silica beads are added. This observation is made in the simple scattering regime (inter-sphere distance four times larger than their radius) and is shown to depend on the concentration of the silica spheres. For a solution of rhodamine B, the enhancement can reach more than 30 %. As complementary experiments show that the fluorescence efficiency is unchanged, we argue that the non-linear absorption is enhanced due to focussing of the incident beam in the near-field of the spheres, a situation previously referred to as photonic (nano-)jets [3]. Our calculations indeed show that for the parameters of the spheres studied near-field focussing leads to an intensity concentration close to the sphere surface. We suggest that these photonic jets could be used to enhance other non-linear optical effects.

Broadband ultrafast spectroscopy using a photonic crystal fiber: application to the photophysics of malachite green.

Femtosecond single-pulsed supercontinua (SC) are produced in a short sub-cm piece of photonic crystal fiber. The SC span from 450 nm to more than 1.1 mum with 1-nJ energy injection. UV light down to 340 nm is observed with increased injection power. Using such a single-pulsed SC we implemented a compact transient absorption spectrometer with broadband detection and 150-fs FWHM time resolution to monitor the ultrafast dynamics of the electronic states of malachite green in ethanol excited to the S(2) state. The full spectral evolution is observed from 450 nm to 1050 nm, with high sensitivity and a signal-to-noise ratio as high as 1000.

Random laser action in organic film during the photopolymerization process.

We report on transient laser action during the photopolymerization process in organic thin films of acrylate monomers doped with a laser dye. The emission spectrum was monitored over a period of time in the direction orthogonal to the incident laser beam which is kept at a constant intensity during the experiments. The emission spectra display the signature of laser action after a certain amount of polymerization. We have also recorded the intensity of fluorescence as well as of the amplified stimulated emission (ASE) using a photodiode. Our results confirmed that all the emission is guided by an increase of the refractive index resulting from the photopolymerization process. The spatial fluctuations in the density of the material are thought to act as micro-cavities leading to a random laser effect.

Quasi-solitonic behavior of self-written waveguides created by photopolymerization.

We investigated the condition of unique self-written channel and multichannel propagation inside bulk photopolymerizable materials. Light was introduced in the medium by a single-mode optical fiber. At a very low beam power of 5 muW , a unique uniform-channel waveguide without any broadening was obtained by polymerization. When the input power is increased to 100 muW , the guide becomes chaotic and multichannel. We connected two fibers separated by a 1-cm distance. The results open the door to studies of the optical and electro-optical properties of photopolymerized guides doped by nonlinear optical chromophores and to possible applications in integrated optical devices.