LHCII can substitute for LHCI as an antenna for photosystem I but with reduced light-harvesting capacity.

Light-harvesting complexes (LHCs) are major constituents of the antenna systems in higher plant photosystems. Four Lhca subunits are tightly bound to the photosystem I (PSI) core complex, forming its outer antenna moiety called LHCI. The Arabidopsis thaliana mutant ΔLhca lacks all Lhca1-4 subunits and compensates for its decreased antenna size by binding LHCII trimers, the main constituent of the photosystem II antenna system, to PSI.

Scanning Fourier transform spectrometer in the visible range based on birefringent wedges.

We introduce a spectrometer capable of measuring sample absorption spectra in the visible regime, based on a time-domain scanning Fourier transform (FT) approach. While infrared FT spectrometers typically employ a Michelson interferometer to create the two delayed light replicas, the proposed apparatus exploits a compact common-mode passive interferometer that relies on the use of birefringent wedges. This ensures excellent path-length stability (∼λ/300) and accuracy, with no need for active feedback or beam tracking.

Broadband pump-probe spectroscopy at 20-MHz modulation frequency.

We introduce an innovative high-sensitivity broadband pump-probe spectroscopy system, based on Fourier-transform detection, operating at 20-MHz modulation frequency. A common-mode interferometer employing birefringent wedges creates two phase-locked delayed replicas of the broadband probe pulse, interfering at a single photodetector. A single-channel lock-in amplifier demodulates the interferogram, whose Fourier transform provides the differential transmission spectrum.

Synthetic niche substrates engineered via two-photon laser polymerization for the expansion of human mesenchymal stromal cells.

The present study reports on the development of an innovative culture substrate, micro-fabricated by two-photon laser polymerization (2PP) in a hybrid organic-inorganic photoresin. It was previously demonstrated that this substrate is able to guide spontaneous homing and colonization of mesenchymal stromal cells by the presence of synthetic microniches. Here, the number of niches covering the culture substrate was increased up to 10% of the total surface.

Exciton-exciton annihilation and biexciton stimulated emission in graphene nanoribbons.

Graphene nanoribbons display extraordinary optical properties due to one-dimensional quantum-confinement, such as width-dependent bandgap and strong electron-hole interactions, responsible for the formation of excitons with extremely high binding energies. Here we use femtosecond transient absorption spectroscopy to explore the ultrafast optical properties of ultranarrow, structurally well-defined graphene nanoribbons as a function of the excitation fluence, and the impact of enhanced Coulomb interaction on their excited states dynamics. We show that in the high-excitation regime biexcitons are formed by nonlinear exciton-exciton annihilation, and that they radiatively recombine via stimulated emission.

Exciton and charge carrier dynamics in few-layer WS2.

Semiconducting transition metal dichalcogenides (TMDs) have been applied as the active layer in photodetectors and solar cells, displaying substantial charge photogeneration yields. However, their large exciton binding energy, which increases with decreasing thickness (number of layers), as well as the strong resonance peaks in the absorption spectra suggest that excitons are the primary photoexcited states. Detailed time-domain studies of the photoexcitation dynamics in TMDs exist mostly for MoS2.

Macrospin dynamics in antiferromagnets triggered by sub-20 femtosecond injection of nanomagnons.

The understanding of how the sub-nanoscale exchange interaction evolves in macroscale correlations and ordered phases of matter, such as magnetism and superconductivity, requires to bridging the quantum and classical worlds. This monumental challenge has so far only been achieved for systems close to their thermodynamical equilibrium. Here we follow in real time the ultrafast dynamics of the macroscale magnetic order parameter in the Heisenberg antiferromagnet KNiF3 triggered by the impulsive optical generation of spin excitations with the shortest possible nanometre wavelength and femtosecond period.

Superatom State-Resolved Dynamics of the Au25(SC8H9)18(-) Cluster from Two-Dimensional Electronic Spectroscopy.

Superatom state-resolved dynamics of the Au25(SC8H9)18(-) monolayer-protected cluster (MPC) were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The electronic ground state of the Au25(SC8H9)18(-) MPC is described by an eight-electron P-like superatom orbital. Hot electron relaxation (200 ± 15 fs) within the superatom D manifold of lowest-unoccupied molecular orbitals was resolved from hot hole relaxation (290 ± 20 fs) in the superatom P states by using 2DES in a partially collinear pump-probe geometry.

Optimal metal domain size for photocatalysis with hybrid semiconductor-metal nanorods.

Semiconductor-metal hybrid nanostructures offer a highly controllable platform for light-induced charge separation, with direct relevance for their implementation in photocatalysis. Advances in the synthesis allow for control over the size, shape and morphology, providing tunability of the optical and electronic properties. A critical determining factor of the photocatalytic cycle is the metal domain characteristics and in particular its size, a subject that lacks deep understanding.

Ultrasensitive Characterization of Mechanical Oscillations and Plasmon Energy Shift in Gold Nanorods.

Mechanical vibrational resonances in metal nanoparticles are intensively studied because they provide insight into nanoscale elasticity and for their potential application to ultrasensitive mass detection. In this paper, we use broadband femtosecond pump-probe spectroscopy to study the longitudinal acoustic phonons of arrays of gold nanorods with different aspect ratios, fabricated by electron beam lithography with very high size uniformity. We follow in real time the impulsively excited extensional oscillations of the nanorods by measuring the transient shift of the localized surface plasmon band.

Photo-Induced Bandgap Renormalization Governs the Ultrafast Response of Single-Layer MoS2.

Transition metal dichalcogenides (TMDs) are emerging as promising two-dimensional (2D) semiconductors for optoelectronic and flexible devices. However, a microscopic explanation of their photophysics, of pivotal importance for the understanding and optimization of device operation, is still lacking. Here, we use femtosecond transient absorption spectroscopy, with pump pulse tunability and broadband probing, to monitor the relaxation dynamics of single-layer MoS2 over the entire visible range, upon photoexcitation of different excitonic transitions.

Elementary Energy Transfer Pathways in Allochromatium vinosum Photosynthetic Membranes.

Allochromatium vinosum (formerly Chromatium vinosum) purple bacteria are known to adapt their light-harvesting strategy during growth according to environmental factors such as temperature and average light intensity. Under low light illumination or low ambient temperature conditions, most of the LH2 complexes in the photosynthetic membranes form a B820 exciton with reduced spectral overlap with LH1. To elucidate the reason for this light and temperature adaptation of the LH2 electronic structure, we performed broadband femtosecond transient absorption spectroscopy as a function of excitation wavelength in A.

Below-gap excitation of semiconducting single-wall carbon nanotubes.

We investigate the optoelectronic properties of the semiconducting (6,5) species of single-walled carbon nanotubes by measuring ultrafast transient transmission changes with 20 fs time resolution. We demonstrate that photons with energy below the lowest exciton resonance efficiently lead to linear excitation of electronic states. This finding challenges the established picture of a vanishing optical absorption below the fundamental excitonic resonance.

Broadband stimulated Raman scattering with Fourier-transform detection.

We propose a new approach to broadband Stimulated Raman Scattering (SRS) spectroscopy and microscopy based on time-domain Fourier transform (FT) detection of the stimulated Raman gain (SRG) spectrum. We generate two phase-locked replicas of the Stokes pulse after the sample using a passive birefringent interferometer and measure by the FT technique both the Stokes and the SRG spectra. Our approach blends the very high sensitivity of single-channel lock-in balanced detection with the spectral coverage and resolution afforded by FT spectroscopy.

Low frequency dynamics of the nitrogenase MoFe protein via femtosecond pump probe spectroscopy - Observation of a candidate promoting vibration.

We have used femtosecond pump-probe spectroscopy (FPPS) to study the FeMo-cofactor within the nitrogenase (N2ase) MoFe protein from Azotobacter vinelandii. A sub-20-fs visible laser pulse was used to pump the sample to an excited electronic state, and a second sub-10-fs pulse was used to probe changes in transmission as a function of probe wavelength and delay time. The excited protein relaxes to the ground state with a ~1.

Modulating Exciton Dynamics in Composite Nanocrystals for Excitonic Solar Cells.

Quantum dots (QDs) represent one of the most promising materials for third-generation solar cells due to their potential to boost the photoconversion efficiency beyond the Shockley-Queisser limit. Composite nanocrystals can challenge the current scenario by combining broad spectral response and tailored energy levels to favor charge extraction and reduce energy and charge recombination. We synthesized PbS/CdS QDs with different compositions at the surface of TiO2 nanoparticles assembled in a mesoporous film.

Enhanced Photogeneration of Polaron Pairs in Neat Semicrystalline Donor-Acceptor Copolymer Films via Direct Excitation of Interchain Aggregates.

We investigate the photogeneration of polaron pairs (PPs) in neat films of the semicrystalline donor-acceptor semiconducting copolymer PCPDTBT. Carefully selecting the solution-processing procedures, we obtain films with different amounts of crystallinity and interchain aggregation. We compare the photogeneration of PPs between the films by monitoring their photoinduced absorption in ultrafast pump-probe experiments, selectively exciting nonaggregated or aggregated polymer chains.

Structure and dynamics of the membrane attaching nitric oxide transporter nitrophorin 7.

Nitrophorins represent a unique class of heme proteins that are able to perform the delicate transportation and release of the free-radical gaseous messenger nitric oxide (NO) in a pH-triggered manner. Besides its ability to bind to phospholipid membranes, the N-terminus contains an additional Leu-Pro-Gly stretch, which is a unique sequence trait, and the heme cavity is significantly altered with respect to other nitrophorins. These distinctive features encouraged us to solve the X-ray crystallographic structures of NP7 at low and high pH and bound with different heme ligands (nitric oxide, histamine, imidazole).

Modeling the high-energy electronic state manifold of adenine: Calibration for nonlinear electronic spectroscopy.

Pump-probe electronic spectroscopy using femtosecond laser pulses has evolved into a standard tool for tracking ultrafast excited state dynamics. Its two-dimensional (2D) counterpart is becoming an increasingly available and promising technique for resolving many of the limitations of pump-probe caused by spectral congestion. The ability to simulate pump-probe and 2D spectra from ab initio computations would allow one to link mechanistic observables like molecular motions and the making/breaking of chemical bonds to experimental observables like excited state lifetimes and quantum yields.

Ultra-broadband 2D electronic spectroscopy of carotenoid-bacteriochlorophyll interactions in the LH1 complex of a purple bacterium.

We investigate the excitation energy transfer (EET) pathways in the photosynthetic light harvesting 1 (LH1) complex of purple bacterium Rhodospirillum rubrum with ultra-broadband two-dimensional electronic spectroscopy (2DES). We employ a 2DES apparatus in the partially collinear geometry, using a passive birefringent interferometer to generate the phase-locked pump pulse pair. This scheme easily lends itself to two-color operation, by coupling a sub-10 fs visible pulse with a sub-15-fs near-infrared pulse.

Stimulated Raman gas sensing by backward UV lasing from a femtosecond filament.

We perform a proof-of-principle demonstration of chemically specific standoff gas sensing, in which a coherent stimulated Raman signal is detected in the direction anticollinear to a two-color laser excitation beam traversing the target volume. The proposed geometry is intrinsically free space as it does not involve back-scattering (reflection) of the signal or excitation beams at or behind the target. A beam carrying an intense mid-IR femtosecond (fs) pulse and a parametrically generated picosecond (ps) UV Stokes pulse is fired in the forward direction.

High energetic excitons in carbon nanotubes directly probe charge-carriers.

Theory predicts peculiar features for excited-state dynamics in one dimension (1D) that are difficult to be observed experimentally. Single-walled carbon nanotubes (SWNTs) are an excellent approximation to 1D quantum confinement, due to their very high aspect ratio and low density of defects. Here we use ultrafast optical spectroscopy to probe photogenerated charge-carriers in (6,5) semiconducting SWNTs.

Communication: SHG-detected circular dichroism imaging using orthogonal phase-locked laser pulses.

We demonstrate a novel method for second harmonic generation-detected circular dichroism (CD) imaging based on the use of phase-locked, temporally delayed femtosecond laser pulses. The polarization state of the fundamental wave was controllably changed over 2π rad by using a birefringent delay line, which provided attosecond inter-pulse delays for orthogonal phase-locked replicas; the achievable phase stability was 14 as. By introducing either a positive or negative delay of ∼667 as, we induced a ±π/2 phase shift between the orthogonally polarized pulses, resulting in left circularly polarized or right circularly polarized light.

Dual fluorescence through Kasha's rule breaking: an unconventional photomechanism for intracellular probe design.

Dual fluorescence is an anomalous photophysical phenomenon observed in very few chromophores in which a two-color radiative process occurs that involves two distinct excited electronic states. To date its observation was linked either to electronic rearrangement of an excited fluorophore leading to two conformers with distinct emissive properties, or to a photochemical modification leading to different fluorescent species. In both cases, emission originates from the lowest excited state of the resulting molecular configurations, in line with the so-called Kasha's rule.

Mode matching in multiresonant plasmonic nanoantennas for enhanced second harmonic generation.

Boosting nonlinear frequency conversion in extremely confined volumes remains a challenge in nano-optics research, but can enable applications in nanomedicine, photocatalysis and background-free biosensing. To obtain brighter nonlinear nanoscale sources, approaches that enhance the electromagnetic field intensity and counter the lack of phase matching in nanoplasmonic systems are often employed. However, the high degree of symmetry in the crystalline structure of plasmonic materials (metals in particular) and in nanoantenna designs strongly quenches second harmonic generation.