Investigating Piezochromic Properties of πconjugated Materials: a combined Raman and DFT Study

Π-conjugated materials have been studied for decades due to their great interest in organic electronics. Among them, piezochromic materials, which exhibit color changes resulting from external pressure or mechanical grinding, become very attractive from a scientific viewpoint owing to their potential applications as pressure-sensing and opticalrecording systems1. The main target of the present work is to develop a joint experimental and theoretical approach able to deliver crucial information for the understanding of the structural effects causing piezochromic changes. To this end, we will focus our attention on two families of -conjugated materials with potential application as sensors. The first one is a family of 9,10-Bis((E)-n(pyrid-2-yl)vinyl) anthracene, BPnVA (n=2 orto-,3 metha- and 4 para-) compounds, see Figure 1. Interestingly, these three compounds with varying position of the nitrogen on the external pyridyl group exhibit different molecular packing modes. Grinding and the application of external pressure on the powder also led to a strong change in their photoluminescence color.2 The second familiy is based on the N,N’-Bis-Boc-3,3’-di(pyren-1yl)-2,2’-biindole compound (compound 1c in Figure 1) which also shows photoluminescence under pressure application. However, the molecular packing induced by this phenomenon is still under study 3. In both cases, it will be also very interesting to determine how temperature affects the vibrational structure of these systems.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Cauliflower mosaic virus is preferentially acquired from the phloem by its aphid vectors

Cauliflower mosaic virus (CaMV) is transmitted in a non-circulative manner by aphids following the helper strategy. Helper proteins P2 and P3 act as a bridge between virions and the aphid cuticle. Electronic monitoring of aphid stylet activities (EPG technique), transmission tests and electron microscopy showed that CaMV is preferentially acquired from the phloem by its most common aphid vectors, Brevycorine brassicae and Myzus persicae. We also found that CaMV is semipersistently transmitted and that the rate of acquisition does not follow a typical bimodal curve. Instead, the virus could be acquired from non-phloem tissues at a low and fairly constant rate after one or more intracellular punctures within a few minutes, but the probability of acquisition rose significantly when aphids reached the phase of committed ingestion from the phloem. The acquisition rate of CaMV did not increase with increasing number of intracellular punctures, but the total duration of intracellular puncture was one of the variables selected by the stepwise logistic regression model used to fit the data that best explained acquisition of CaMV. Furthermore, aphids reaching the phloem faster had a higher probability of acquiring the virus. Our results support the hypothesis that multiple intracellular punctures of epidermal and mesophyll cells result in loading aphids with the CaMV-encoded aphid transmission factor (P2), and that aphids, in most cases, subsequently acquire CaMV particles during phloem sap ingestion. Consistently, immunoelectron microscopy showed that P3–virions are frequently found in the sieve element lumen, whereas P2 could not be detected.We are indebted to the Spanish Ministry of Science and Technology (Research Grant, no. AGL:2000-2006) for funding this work. Also, we acknowledge the Comunidad Autónoma de Madrid (Spain) and CAPES (Brazil) for funding the fellowships awarded to I.P. and S.L., respectively. M.D. was awarded a fellowship from the ACI-JC of the French Ministry for Research. We thank Takii Ltd seed company for kindly providing turnip ‘Just Right’ seedsPeer reviewe

Theoretical study of the dynamics of atomic hydrogen adsorbed on graphene multilayers

We present a theoretical study of the dynamics of H atoms adsorbed on graphene bilayers with Bernal stacking. First, through extensive density functional theory calculations, including van der Waals Interactions, we obtain the activation barriers involved in the desorption and migration processes of a single H atom. These barriers, along with attempt rates and the energetics of H pairs, are used as input parameters in kinetic Monte Carlo simulations to study the time evolution of an initial random distribution of adsorbed H atoms. The simulations reveal that, at room temperature, H atoms occupy only one sublattice before they completely desorb or form clusters. This sublattice selectivity in the distribution of H atoms may last for sufficiently long periods of time upon lowering the temperature down to 0 ◦C. The final fate of the H atoms, namely, desorption or cluster formation, depends on the actual relative values of the activation barriers which can be tuned by doping. In some cases, a sublattice selectivity can be obtained for periods of time experimentally relevant even at room temperature. This result shows the possibility for observation and applications of the ferromagnetic state associated with such distributionThis work was supported by MINECO under Grant Nos. FIS2013-47328 and FIS2012-37549, by CAM under Grant Nos. S2013/MIT-3007, P2013/MIT-2850, and by Generalitat Valenciana under Grant PROMETEO/2012/01

Piezochromic properties of a D-A-D platform: A joint experimental and theoretical perspective

Organic π-conjugated molecules with mechanochromic luminescence properties have attracted great interest in the last two decades due to their numerous applications in the optoelectronic field, such as sensors, probes and security inks. Materials that modify their colour under pressure are known as piezochromic materials. Usually, this variation is provoked by changes in the molecular structure, for example, crystal-to-amorphous phase transitions, modifications in dihedral angles or bond distances, and intermolecular interactions. The molecule proposed in this study is a TADF (Thermally activated delayed fluorescence) U-shaped molecule composed by two donors and one acceptor (D-A-D) units with a π-conjugated skeleton [1]. It was synthetized as a powder which under different crystallization methods gives rise to different conformers varying the dihedral angle of the bond that links the D and A units. The donors are two phenothiazine units and the acceptor is a dibenzo[a,j]phenazine unit located in the central core. Two different conformers have been analysed: the quasi equatorial - quasi equatorial (denoted as 1R) and the quasi axial - quasi axial (denoted as 1Y). In this project, we study the configurational changes triggering the piezochromic effects combining density functional theory (DFT) calculations with Raman spectroscopy experiments of the 1R and 1Y conformers during heating or in compression via a sapphire anvil cell [2]. Both show pressure and temperature dependence properties. Besides, these changes are reversible meaning that when the stimuli stop they revert to its original conformation. When these molecules are exposed to different ambient (like pressure or temperature variations) they evolved to a third conformer with an intermediate dihedral angle that results in different Raman, emission and absorption behaviour.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Impact of early vs. delayed initiation of dutasteride/tamsulosin combination therapy on the risk of acute urinary retention or BPH-related surgery in LUTS/BPH patients with moderate-to-severe symptoms at risk of disease progression

Purpose: To evaluate the effect of delayed start of combination therapy (CT) with dutasteride 0.5 mg and tamsulosin 0.4 mg on the risk of acute urinary retention or benign prostatic hyperplasia (BPH)-related surgery (AUR/S) in patients with moderate-to-severe lower urinary tract symptoms (LUTS) at risk of disease progression. Methods: Using a time-to-event model based on pooled data from 10,238 patients from Phase III/IV dutasteride trials, clinical trial simulations (CTS) were performed to assess the risk of AUR/S up to 48 months in moderate-to-severe LUTS/BPH patients following immediate and delayed start of CT for those not responding to tamsulosin monotherapy. Simulation scenarios (1300 subjects/arm) were investigated, including immediate start (reference) and alternative delayed start (six scenarios 1–24 months). AUR/S incidence was described by Kaplan–Meier survival curves and analysed using log-rank test. The cumulative incidence of events as well as the relative and attributable risks were summarised stratified by treatment. Results: Survival curves for patients starting CT at month 1 and 3 did not differ from those who initiated CT immediately. By contrast, significant differences (p < 0.001) were observed when switch to CT occurs ≥ 6 months from the initial treatment. At month 48, AUR/S incidence was 4.6% vs 9.5%, 11.0% and 11.3% in patients receiving immediate CT vs. switchers after 6, 12 and 24 months, respectively. Conclusions: Start of CT before month 6 appears to significantly reduce the risk of AUR/S compared with delayed start by ≥ 6 months. This has implications for the treatment algorithm for men with LUTS/BPH at risk of disease progression

Capacitance spectroscopy in quantum dots: Addition spectra and decrease of tunneling rates

A theoretical study of single electron capacitance spectroscopy in quantum dots is presented. Exact diagonalizations and the unrestricted Hartree-Fock approximation have been used to shed light over some of the unresolved aspects. The addition spectra of up to 15 electrons is obtained and compared with the experiment. We show evidence for understanding the decrease of the single electron tunneling rates in terms of the behavior of the spectral weight function. (To appear in Phys. Rev. B (Rapid Comm.))Comment: 10 pages, Revtex, hard copy or PostScript Figures upon request on [email protected]

Estrategias bioanalíticas en estudios metalómicos de fármacos de platino

En este artículo se muestra el potencial que presentan las modernas estrategias bioanalíticas en estudios metalómicos de fármacos de platino. La combinación de técnicas de separación multidimensionales cromatográficas y/o electroforéticas con la espectrometría de masas atómica ICP-MS y molecular ESI-MS/MS se presenta como una valiosa alternativa en este tipo de estudios