Mixing of electronic states in pentacene adsorption on copper

By combining experimental and theoretical approaches, we study the adsorption of pentacene on copper as a model for the coupling between aromatic molecules and metal surfaces. Our results for the interface electronic structure are not compatible with a purely physisorption picture, which is conventionally employed for such systems. Nay, we demonstrate electronic mixing between molecular orbitals and metal electronic states.     

Angle-independent and multi-dimensional myocardial elastography--from theory to clinical validation

The angle-independent myocardial elastography, which shows good performance in our proposed theoretical framework using a three-dimensional, ultrasonic image formation model based on well-established, 3D finite-element, canine, left-ventricular models in both normal and left-circumflex ischemic cases, is employed as well as validated in vivo to assess the contractility of normal and pathological myocardia. Angle-independent myocardial elastography consists of: (1) iterative estimation of in-plane and out-of-plane cumulative displacements during systole using 1D cross-correlation and recorrelation techniques in a 2D search; (2) calculation of in-plane finite strains from the in-plane cumulative motion; and (3) computation of in-plane principal strains from the finite strains by eigen decomposition with a classification strategy. The in vivo raw data of healthy and pathological human left ventricles were acquired at 136 fps in a short-axis echocardiographic view. Similar to theory, the elastographic estimates in normal clinical cases showed radial wall thickening and circumferential shortening during systole through principal strain imaging, while those in a pathological case underwent opposite strains. The feasibility of angle-independent myocardial elastography with an automated contour tracking method was hereby demonstrated through imaging of the myocardial deformation, and principal strains were proven essential in the reliable characterization and differentiation of abnormal from normal myocardia, without any angular dependence.     

Electrochemical Approach for the Production of Layered Double Hydroxides with a Well-Defined Co/MeIII Ratio

Layered double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, the electrochemical approach does not usually allow for a fine control of the M^II/M^III ratio in the synthesized material. By employing a recently proposed potentiodynamic method, LDH films of controlled composition are herein prepared with good reproducibility, using different ratios of the trivalent (Fe or Al) to bivalent (Co) cations in the electrolytic solution. All the obtained materials are shown to be effective oxygen evolution reaction (OER) catalysts, and are thoroughly characterized by a multi-technique approach, including FE-SEM, XRD, Raman, AES and a wide range of electrochemical procedures.     

Consecutive Supramolecular Polymerization of a Rylene-Based Twistacene

The synthesis and self-assembling features of twistacene 1 are reported. The supramolecular polymerization of 1 displays a consecutive pathway to afford slipped ( AggI ) and rotationally displaced ( AggII ) aggregates conditioned by the formation of intramolecularly H-bonded pseudocycles. In methylcyclohexane, both AggI and AggII are highly stable and the interconversion of the kinetically controlled AggI into the thermodynamically controlled AggII takes several weeks to occur. The utilization of toluene as solvent changes the energetic level for both aggregates and favors a faster conversion of AggI into AggII within a period of minutes. This conversion can be accelerated by the addition of seeds. Furthermore, concentration dependent kinetic studies demonstrate the consecutive character of the supramolecular polymerization of 1 .     

Applicability of Microaerobic Technology to Enhance BTEX Removal from Contaminated Waters

As the addition of low concentrations of oxygen can favor the initial degradation of benzene, toluene, ethylbenzene, and xylenes (BTEX) compounds, this work verified the applicability of the microaerobic technology to enhance BTEX removal in an anaerobic bioreactor supplemented with high and low co-substrate (ethanol) concentrations. Additionally, structural alterations on the bioreactor microbiota were assessed throughout the experiment. The bioreactor was fed with a synthetic BTEX-contaminated water (~ 3 mg L^?1 of each compound) and operated at a hydraulic retention time of 48 h. The addition of low concentrations of oxygen (1.0 mL min^?1 of atmospheric air at 27 °C and 1 atm) assured high removal efficiencies (> 80%) for all compounds under microaerobic conditions. In fact, the applicability of this technology showed to be viable to enhance BTEX removal from contaminated waters, especially concerning benzene (with a 30% removal increase), which is a very recalcitrant compound under anaerobic conditions. However, high concentrations of ethanol adversely affected BTEX removal, especially benzene, under anaerobic and microaerobic conditions. Finally, although bacterial community richness decreased at low concentrations of ethanol, in general, the bioreactor microbiota could deal with the different operational conditions and preserved its functionality during the whole experiment.     

An analytic approach to stochastic Volterra equations with completely monotone kernels

We apply the semigroup setting of Desch and Miller to a class of stochastic integral equations of Volterra type with completely monotone kernels with a multiplicative noise term; the corresponding equation is an infinite dimensional stochastic equation with unbounded diffusion operator that we solve with the semigroup approach of Da Prato and Zabczyk. As a motivation of our results, we study an optimal control problem when the control enters the system together with the noise.      

Isotope dilution GC-MS routine method for the determination of butyltin compounds in water

A standard GC-MS instrument with electron impact ionisation has been used to develop a fast, simple and reliable method for the simultaneous determination of monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) in water samples. Isotope dilution analysis (IDA) is used for the determination of species, taking advantage of a commercially available spike solution containing a mixture of MBT, DBT and TBT enriched in ¹¹⁹Sn. Method detection limits for 100-mL samples were between 0.18 and 0.25 ng L⁻¹ for the three butyltin compounds with typical RSD between 2 and 4% at levels between 100 and 10 ng L⁻¹, respectively. Recovery of tin species in spiked samples (natural water, wastewater and seawater) was quantitative. The stability of butyltin compounds in collected seawater samples was also studied. The addition of a 1% (v/v) glacial acetic acid preserved tin species in the samples for at least 5 days at room temperature. The IDA method was finally implemented in a routine testing laboratory and it was subsequently accredited by the Spanish National Accreditation Body according to the requirements of UNE-EN ISO/IEC 17025.     

Investigation of anthropic effects connected with metal ions concentration, organic matter and grain size in Bormida river sediments

An investigation on the sediment composition and grain size was carried out along the Bormida river (Piedmont, Northern Italy). The samples were taken both in the riverbed and on its banks. Multivariate statistical exploratory methods permitted to identify possible sources of primary pollution. In particular, principal component analysis (PCA) showed that there are probably at least three anthropogenic main causes of pollution, one connected with Cr, Ni and Sn, the second with cadmium and the last one with mercury. Some correlations were found between heavy metal ion concentrations and organic matter and/or the sediment grain size. Differences between the samples collected in the riverbed and on the banks were identified and the relationships between the principal components and the distance of the samples from the riverbed and from the hot spot represented by the ACNA industrial site were also analyzed.     

Revealing Excited-State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited-state trajectories of a diplatinum complex featuring photo-activated metal–metal σ-bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide-angle X-ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited-state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non-equilibrium processes along excited-state trajectories involving multiple excited-state PESs.