0000000000056140
AUTHOR
Giulio Cerullo
Electrostatic Tuning of the Ligand Binding Mechanism by Glu27 in Nitrophorin 7
AbstractNitrophorins (NP) 1–7 are NO-carrying heme proteins found in the saliva of the blood-sucking insect Rhodnius prolixus. The isoform NP7 displays peculiar properties, such as an abnormally high isoelectric point, the ability to bind negatively charged membranes, and a strong pH sensitivity of NO affinity. A unique trait of NP7 is the presence of Glu in position 27, which is occupied by Val in other NPs. Glu27 appears to be important for tuning the heme properties, but its influence on the pH-dependent NO release mechanism, which is assisted by a conformational change in the AB loop, remains unexplored. Here, in order to gain insight into the functional role of Glu27, we examine the ef…
π-Extended Pyrene-Fused Double [7]Carbohelicene as a Chiral Polycyclic Aromatic Hydrocarbon
A π-extended double [7]carbohelicene 2 with fused pyrene units was synthesized, revealing considerable intra- and intermolecular π–π interactions as confirmed with X-ray crystallography. As compared to the previous double [7]carbohelicene 1, the π-extended homologue 2 demonstrated considerably red-shifted absorption with an onset at 645 nm (1: 550 nm) corresponding to a smaller optical gap of 1.90 eV (1: 2.25 eV). A broad near-infrared emission from 600 to 900 nm with a large Stokes shift of ∼100 nm (2.3 × 103 cm–1) was recorded for 2, implying formation of an intramolecular excimer upon excitation, which was corroborated with femtosecond transient absorption spectroscopy. Moreover, 2 revea…
Strong Coupling of Coherent Phonons to Excitons in Semiconducting Monolayer MoTe$_2$
The coupling of the electron system to lattice vibrations and their time-dependent control and detection provides unique insight into the non-equilibrium physics of semiconductors. Here, we investigate the ultrafast transient response of semiconducting monolayer 2$H$-MoTe$_2$ encapsulated with $h$BN using broadband optical pump-probe microscopy. The sub-40-fs pump pulse triggers extremely intense and long-lived coherent oscillations in the spectral region of the A' and B' exciton resonances, up to $\sim$20% of the maximum transient signal, due to the displacive excitation of the out-of-plane $A_{1g}$ phonon. Ab-initio calculations reveal a dramatic rearrangement of the optical absorption of…
Acoustic dynamics of network-forming glasses at mesoscopic wavelengths
The lack of long-range structural order in amorphous solids induces well known thermodynamic anomalies, which are the manifestation of distinct peculiarities in the vibrational spectrum. Although the impact of such anomalies vanishes in the long wavelength, elastic continuum limit, it dominates at length scales comparable to interatomic distances, implying an intermediate transition regime still poorly understood. Here we report a study of such mesoscopic domains by means of a broadband version of picosecond photo-acoustics, developed to coherently generate and detect hypersonic sound waves in the sub-THz region with unprecedented sampling efficiency. We identify a temperature-dependent fra…
Structure and dynamics of the membrane attaching nitric oxide transporter nitrophorin 7 [v1; ref status: indexed, http://f1000r.es/508]
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). The overall fold of the lipocalin motif is well preserved in the different X-r…
Laser-driven quantum magnonics and terahertz dynamics of the order parameter in antiferromagnets
The impulsive generation of two-magnon modes in antiferromagnets by femtosecond optical pulses, so-called femto-nanomagnons, leads to coherent longitudinal oscillations of the antiferromagnetic order parameter that cannot be described by a thermodynamic Landau-Lifshitz approach. We argue that this dynamics is triggered as a result of a laser-induced modification of the exchange interaction. In order to describe the oscillations we have formulated a quantum mechanical description in terms of magnon pair operators and coherent states. Such an approach allowed us to} derive an effective macroscopic equation of motion for the temporal evolution of the antiferromagnetic order parameter. An impli…
Study of Mechanisms of Light-Induced Dissociation of Ru(dcbpy)(CO)2I2 in Solution down to 20 fs Time Resolution
Mechanisms of the light-induced ligand exchange reaction of (trans-I) Ru(dcbpy)(CO)2I2 (dcbpy = 4,4'-dicarboxylic acid-2,2'-bipyridine) in ethanol have been studied by transient absorption spectroscopy. Ultraviolet 20 fs excitation pulses centered at 325 nm were used to populate a vibrationally hot excited pi bipyridyl state of the reactant that quickly relaxes to a dissociative Ru-I state resulting in the release of one of the carbonyl groups. Quantum yield measurements have indicated that about 40% of the initially exited reactant molecules form the final photoproduct. A 62 fs rise component in the transient absorption (TA) signal was observed at all probe wavelengths in the visible regio…
Strong Exciton-Coherent Phonon Coupling in Single-Layer MoS2
Broadband transient absorption with sub-20fs temporal resolution, supported by ab-initio calculations, quantitatively provides the strength of exciton-coherent phonon coupling in 1L-MoS2, showing a resonant profile around the C exciton.
Structure and dynamics of the membrane attaching nitric oxide transporter nitrophorin 7 [v2; ref status: indexed, http://f1000r.es/5p1]
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 of NP7, a member of the NO transporter nitrophorin family, 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). The overall fold of…
Intravalley spin-flip relaxation dynamics in single-layer WS2
Two-dimensional Transition Metal Dichalcogenides (TMDs) have been widely studied because of the peculiar electronic band structure and the strong excitonic effects [1]. In these materials the large spin-orbit coupling lifts the spin degeneracy of the valence (VB) and the conduction band (CB) giving rise to the A and B interband excitonic transitions. In monolayer WS2, the spins of electrons in the lowest CB and in the highest VB at K/K' point of the Brillouin zone are antiparallel resulting in an intravalley dark exciton state at a lower energy than the bright exciton, see left panel of Fig.1. On the one hand, the presence of dark excitons has been revealed indirectly from the observation o…
Tuning the Ultrafast Response of Fano Resonances in Halide Perovskite Nanoparticles
International audience; The full control of the fundamental photophysics of nanosystems at frequencies as high as few THz is key for tunable and ultrafast nanophotonic devices and metamaterials. Here we combine geometrical and ultrafast control of the optical properties of halide perovskite nanoparticles, which constitute a prominent platform for nanophotonics. The pulsed photoinjection of free carriers across the semiconducting gap leads to a subpicosecond modification of the far-field electromagnetic properties that is fully controlled by the geometry of the system. When the nanoparticle size is tuned so as to achieve the overlap between the narrowband excitons and the geometry-controlled…
Regioselective Hydrogenation of a 60-Carbon Nanographene Molecule toward a Circumbiphenyl Core.
Regioselective peripheral hydrogenation of a nanographene molecule with 60 contiguous sp2 carbons provides unprecedented access to peralkylated circumbiphenyl (1). Conversion to the circumbiphenyl core structure was unambiguously validated by MALDI-TOF mass spectrometry, NMR, FT-IR, and Raman spectroscopy. UV–vis absorption spectra and DFT calculations demonstrated the significant change of the optoelectronic properties upon peripheral hydrogenation. Stimulated emission from 1, observed via ultrafast transient absorption measurements, indicates potential as an optical gain material.
Real-time observation of the intravalley spin-flip process in single-layer WS2
We use helicity-resolved transient absorption spectroscopy to track intravalley scattering dynamics in monolayer WS2. We find that spin-polarized carriers scatter from upper to lower conduction band by reversing their spin orientation on a sub-ps timescale.
Optical tuning of dielectric nanoantennas for thermo-optically reconfigurable nonlinear metasurfaces
We demonstrate optically tunable control of second-harmonic generation in all-dielectric nanoantennas: by using a control beam that is absorbed by the nanoresonator, we thermo-optically change the refractive index of the radiating element to modulate the amplitude of the second-harmonic signal. For a moderate temperature increase of roughly 40 K, modulation of the efficiency up to 60% is demonstrated; this large tunability of the single meta-atom response paves the way to exciting avenues for reconfigurable homogeneous and heterogeneous metasurfaces.
Strongly Coupled Coherent Phonons in Single-Layer MoS 2
We present a transient absorption setup combining broadband detection over the visible-UV range with high temporal resolution ($\sim$20fs) which is ideally suited to trigger and detect vibrational coherences in different classes of materials. We generate and detect coherent phonons (CPs) in single layer (1L) MoS$_2$, as a representative semiconducting 1L-transition metal dichalcogenide (TMD), where the confined dynamical interaction between excitons and phonons is unexplored. The coherent oscillatory motion of the out-of-plane $A'_{1}$ phonons, triggered by the ultrashort laser pulses, dynamically modulates the excitonic resonances on a timescale of few tens fs. We observe an enhancement by…
Electron Transfer from Organic Aminophenyl Acid Sensitizers to Titanium Dioxide Nanoparticle Films
Electron transfer from three conjugated amino-phenyl acid dyes to titanium and aluminum oxide nanocrystalline films was studied by using transient absorption spectroscopy with sub 20 fs time-resolution over the visible spectral region. All the dyes attached to TiO2 showed long-lived ground state bleach signals indicative of formation of new species. Global analysis of the transient kinetics of the dyes on TiO2 revealed stimulated emission decays of about 40 fs and less than 300 fs assigned to electron injection. The same dyes on Al2O3 substrates displayed long stimulated emission decays (ns) suggesting that electron transfer is blocked in this high band gap semiconductor. For two of the dye…
CCDC 1914718: Experimental Crystal Structure Determination
Related Article: Yunbin Hu, Giuseppe M. Paternò, Xiao-Ye Wang, Xin-Chang Wang, Michele Guizzardi, Qiang Chen, Dieter Schollmeyer, Xiao-Yu Cao, Giulio Cerullo, Francesco Scotognella, Klaus Müllen, Akimitsu Narita|2019|J.Am.Chem.Soc.|141|12797|doi:10.1021/jacs.9b05610