Ultrafast charge transfer and vibronic coupling in a laser-excited hybrid inorganic/organic interface

Hybrid interfaces formed by inorganic semiconductors and organic molecules are intriguing materials for opto-electronics. Interfacial charge transfer is primarily responsible for their peculiar electronic structure and optical response. Hence, it is essential to gain insight into this fundamental process also beyond the static picture. Ab initio methods based on real-time time-dependent density-functional theory coupled to the Ehrenfest molecular dynamics scheme are ideally suited for this problem. We investigate a laser-excited hybrid inorganic/organic interface formed by the electron acceptor molecule 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4TCNQ) physisorbed on a hydrogenated silicon cluster, and we discuss the fundamental mechanisms of charge transfer in the ultrashort time window following the impulsive excitation. The considered interface is p-doped and exhibits charge transfer in the ground state. When it is excited by a resonant laser pulse, the charge transfer across the interface is additionally increased, but contrary to previous observations in all-organic donor/acceptor complexes, it is not further promoted by vibronic coupling. In the considered time window of 100 fs, the molecular vibrations are coupled to the electron dynamics and enhance intramolecular charge transfer. Our results highlight the complexity of the physics involved and demonstrate the ability of the adopted formalism to achieve a comprehensive understanding of ultrafast charge transfer in hybrid materials

XAV939-mediated ARTD activity inhibition in human MB cell lines

Diphtheria toxin-like ADP-ribosyltransferases 1 and 5 (ARTD-1, ARTD-5) are poly ADP-ribose enzymes (PARP) involved in non-homologous end-joining (NHEJ), which is the major pathway of double-strand break (DSB) repair. In addition, ARTD-5, or Tankyrase (TNKS), is a positive regulator of the WNT signaling implicated in the development and biological behavior of many neoplasms, such as Medulloblastoma (MB), in which radiotherapy is an essential part of the treatment. The use of radiosensitizing agents may improve the therapeutic index in MB patients by increasing the efficacy of radiotherapy, while reducing toxicity to the neuroaxis. ARTD-5 seems to be a good molecular target for improving the current treatment of MB. In this study, we used the small molecule XAV939, a potent ARTD-5 inhibitor with a slight affinity for ARTD-1, in different human MB cell lines. XAV939 inhibited the WNT pathway and DNA-PKcs in our MB cells, with many biological consequences. The co-administration of XAV939 and ionizing radiations (IR) inhibited MB cells proliferation and clonogenic capacity, decreased their efficacy in repairing DNA damage, and increased IR-induced cell mortality. In conclusion, our in vitro data show that XAV939 could be a very promising small molecule in MB treatment, and these results lay the basis for further in vivo studies with the aim of improving the current therapy available for MB patients

Weighted multivariate curve resolution – alternating least squares based on sample relevance

Alternating least squares, within the multivariate curve resolution framework has seen a lot of practical applications and shows its distinction with its relatively simple and flexible implementation. However, the limitations of least squares should be considered carefully when deviating from the standard assumed data structure. Within this work we highlight the effects of noise in the presence of minor components, and we propose a novel weighting scheme within the weighted multivariate curve-resolution-alternating least squares framework, to resolve it. Two simulated and one Raman imaging case is investigated, by comparing the novel methodology against standard multivariate curve resolution-alternating least squares and essential spectral pixel selection. A trade-off is observed between current methods, while the novel weighting scheme demonstrates a balance, where the benefits of the previous two methods are retained

Potential-field inversion for a layer with uneven thickness: the Tyrrhenian Sea density model

Inversion of large-scale potential-field anomalies, aimed at determining density or magnetization, is usually made in the Fourier domain. The commonly adopted geometry is based on a layer of constant thickness, characterized by a bottom surface at a fixed distance from the top surface. We propose a new method to overcome this limiting geometry, by inverting in the usual iterating scheme using top and bottom surfaces of differing, but known shapes. Randomly generated synthetic models will be analyzed, and finally performance of this method will be tested on real gravity data describing the isostatic residual anomaly of the Southern Tyrrhenian Sea in Italy. The final result is a density model that shows the distribution of the oceanic crust in this region, which is delimited by known structural elements and appears strongly correlated with the oceanized abyssal basins of Vavilov and Marsili

Detph-to-the-bottom Optimization for Potential-field Data Inversion

We show an algorithm for the linear inversion of 2D surface magnetic data to obtain 3D models of the susceptibility of the source. After showing a novel characterization of the ambiguity domain in the Fourier space, which has a simple geometrical interpretation, we will demonstrate that a depth-weighting function is useful to significantly reduce the ambiguity domain in order to characterize the main source properties. The forward model is discretized by a mesh of prismatic cells with constant magnetization that allows the recovery of a complete 3D generating source. As the number of cells are normally grater than the amount of available data, we are left with an underdetermined linear inverse problem, which can be regularized in order to obtain an unique solution by a depth-weighting function, adapted from Li and Oldenburg (1996) to close the source towards its bottom. The main novelty of this method is a first-stage optimization that gives information about the depth-to-the-bottom (dtb) of the generating source. This parameter permits both the evaluation of the appropriate vertical extension of the mesh, and the definition of the shape of the regularizing depth-weighting distribution. The adopted method is suitable under appropriate changes to deal also with gravity data. After showing which kind of a priori information is introduced by this particular regularization, we will describe its limits and its possible improvements and then we will show the results of some synthetic tests. As a final application we will show the 3D magnetic model of an interesting volcanic region in Italy

Depth-to-the-bottom optimization for potential field inversion

We present an algorithm for the linear inversion of 2D surface magnetic data to obtain 3D models of the susceptibility of the source. The forward model is discretized by a mesh of prismatic cells with constant magnetization that allows the recovery of a complete 3D generating source....

Magnification of Plasmon Resonances in Monolayer MoS2_{2} via Conjugated Molecular Adsorbates

The adsorption of carbon-conjugated molecules represents an established route to tune the electronic and optical properties of transition metal dichalcogenide (TMDC) monolayers. Here, we demonstrate from first principles that such a functionalization with prototypical compounds pyrene and tetracene can also enhance the magnitude of selected plasmon resonances in a MoS$_2$ single sheet, without significantly altering their energy and dispersion. Our proof-of-principle results indicate that such a magnification can be achieved by proper alignment of the molecules with respect to the direction of the transferred momentum. The distinct signatures in the loss function of the interface compared to those of its constituents suggest not only the presence of non-negligible interactions between them but also the possibility of using electron energy loss spectroscopy to detect the presence and the orientation of molecular adsorbates on TMDCs