Spectroscopic fingerprints of iron-coordinated cobalt and iron porphyrin layers on graphene

Achieving design capabilities of monolayer 2D functional catalysts represents a challenging perspective. Coordinated single metal atom sites can offer tailored electronic configuration, ligation geometries, chemical activity and selectivity, together with stability. We report spectroscopic evidence of the formation of a 2D metal-organic framework supported by a single graphene sheet in which coordination among Tetra-Pyridyl-Porphyrins (TPyPs) is spontaneously obtained by exploiting single iron atoms. The spectroscopic characterization, together with ab initio methods, reveals that metal inter-molecular coordination occurs via the terminal nitrogen atoms contained in the pyridinic residues of adjacent TPyPs. Interestingly, the peripheral coordination of metal atoms is found to affect the electronic configuration of the porphyrins core. Due to the chemical stability of the supporting graphene layer, its weak interaction with the metal-organic framework, and the known electrochemical activity of the latter, this system represents an optimal candidate for the design and engineering of prototype 2D electrocatalytic materials

Influence of N-Substituents on the Adsorption Geometry of OH-Functionalized Chiral N-Heterocyclic Carbenes

Adsorption of chiral molecules on heterogeneous catalysts is a simple approach for inducing an asymmetric environment to enable enantioselective reactivity. Although the concept of chiral induction is straightforward, its practical utilization is far from simple, and only a few examples toward the successful chiral induction by surface anchoring of asymmetric modifiers have been demonstrated so far. Elucidating the factors that lead to successful chiral induction is therefore a crucial step for understanding the mechanism by which chirality is transferred. Herein, we identify the adsorption geometry of OH-functionalized N-heterocyclic carbenes (NHCs), which are chemical analogues to chiral modifiers that successfully promoted α-arylation reactions once anchored on Pd nanoparticles. Polarized near-edge X-ray absorption fine structure (NEXAFS) measurements on Pd(111) revealed that NHCs that were associated with low enantioselectivity were characterized with a well-ordered structure, in which the imidazole ring was vertically positioned and the OH-functionalized side arms were flat-lying. OH-functionalized NHCs that were associated with high enantioselectivity revealed a disordered/flexible adsorption geometry, which potentially enabled better interaction between the OH group and the prochiral reactant

EMG-Based Characterization of Walking Asymmetry in Children with Mild Hemiplegic Cerebral Palsy

5 May 2019; Accepted: 24 June 2019; Published: 27 June 2019 Abstract: Hemiplegia is a neurological disorder that is often detected in children with cerebral palsy. Although many studies have investigated muscular activity in hemiplegic legs, few EMG-based findings focused on una ected limb. This study aimed to quantify the asymmetric behavior of lower-limb-muscle recruitment during walking in mild-hemiplegic children from surface-EMG and foot-floor contact features. sEMG signals from tibialis anterior (TA) and gastrocnemius lateralis and foot-floor contact data during walking were analyzed in 16 hemiplegic children classified as W1 according to Winter’ scale, and in 100 control children. Statistical gait analysis, a methodology achieving a statistical characterization of gait by averaging surface-EMG-based features, was performed. Results, achieved in hundreds of strides for each child, indicated that in the hemiplegic side with respect to the non-hemiplegic side, W1 children showed a statistically significant: decreased number of strides with normal foot-floor contact; decreased stance-phase length and initial-contact sub-phase; curtailed, less frequent TA activity in terminal swing and a lack of TA activity at heel-strike. The acknowledged impairment of anti-phase eccentric control of dorsiflexors was confirmed in the hemiplegic side, but not in the contralateral side. However, a modified foot-floor contact pattern is evinced also in the contralateral side, probably to make up for balance requirements

Interplay between Hydrogen Bonding and Molecule-Substrate Interactions in the Case of Terephthalic Acid Molecules on Cu(001) Surfaces

The adsorption and self-assembling properties of terephthalic acid (TPA) molecules deposited on Cu(001) at room temperature have been systematically studied using both experimental and theoretical tools. The system forms two phases at room temperature, the metastable β-phase and the stable 3×3 one. In the case of the β phase, the low-energy electron diffraction and scanning-tunneling microscopy (STM) results indicate that the β phase has a (9 √ 2×2 √ 2)R45◦ unit cell with exactly the same molecular coverage as the 3×3 phase. In addition, the high-resolution X-ray photoelectron spectroscopy O1s spectra indicate that the irreversible β → 3 × 3 transition involves the following two processes: i) deprotonation of the complete carboxyl groups remaining in the metastable phase and ii) re-arrangement of the molecules into the 3×3 configuration. On the other hand, we explored possible molecular configurations for the β phase with different degree of deprotonation (including structures with Cu adatoms) by means of density functional theory calculations. Our theoretical results indicate the formation of strong bonds between the O atoms in carboxylates and the Cu atoms of the surface, which causes a bending of the molecules and a buckling of the first Cu layer. In the 3 × 3 phases, we show that the bending produces observable effects in the molecular STM images. We also observed that the strong interaction between the carboxylates and the Cu atoms at the step edges drives the reorientation of the surface steps along the crystallographic directions.Fil: Fuhr, Javier Daniel. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Carrera, Alvaro Daniel. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Murillo Quiros, Natalia Maria. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Cristina, Lucila Josefina. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Cossaro, Albano. Consiglio Nazionale delle Ricerche. Istituto Officina dei Materiali; ItaliaFil: Verdini, Alberto. Consiglio Nazionale delle Ricerche. Istituto Officina dei Materiali; ItaliaFil: Floreano, Luca. Consiglio Nazionale delle Ricerche. Istituto Officina dei Materiali; ItaliaFil: Gayone, Julio Esteban. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Ascolani, Hugo del Lujan. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Decacyclene Trianhydride at Functional Interfaces: An Ideal Electron Acceptor Material for Organic Electronics

We report the interface energetics of decacyclene trianhydride (DTA) monolayers on top of two distinct model surfaces, namely, Au(111) and Ag(111). On the latter, combined valence band photoemission and X-ray absorption measurements that access the occupied and unoccupied molecular orbitals, respectively, reveal that electron transfer from substrate to surface sets in. Density functional theory calculations confirm our experimental findings and provide an understanding not only of the photoemission and X-ray absorption spectral features of this promising organic semiconductor but also of the fingerprints associated with the interface charge transfer

Fluorination of vertically aligned carbon nanotubes:from CF4 plasma chemistry to surface functionalization

The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT) is correlated to the CF4 plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region) on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface. The samples suffer a limited ageing effect, with a small loss of fluorine functionalities after two weeks in ambient conditions

Length-Independent Charge Transport in Chimeric Molecular Wires

Advanced molecular electronic components remain vital for the next generation of miniaturized integrated circuits. Thus, much research effort has been devoted to the discovery of lossless molecular wires, for which the charge transport rate or conductivity is not attenuated with length in the tunneling regime. Herein, we report the synthesis and electrochemical interrogation of DNA-like molecular wires. We determine that the rate of electron transfer through these constructs is independent of their length and propose a plausible mechanism to explain our findings. The reported approach holds relevance for the development of high-performance molecular electronic components and the fundamental study of charge transport phenomena in organic semiconductors

Room-temperature on-spin-switching and tuning in a porphyrin-based multifunctional interface

Molecular interfaces formed between metals and molecular compounds offer a great potential as building blocks for future opto-electronics and spintronics devices. Here, a combined theoretical and experimental spectro-microscopy approach is used to show that the charge transfer occurring at the interface between nickel tetraphenyl porphyrins and copper changes both spin and oxidation states of the Ni ion from [Ni(II), S = 0] to [Ni(I), S = 1/2]. The chemically active Ni(I), even in a buried multilayer system, can be functionalized with nitrogen dioxide, allowing a selective tuning of the electronic properties of the Ni center that is switched to a [Ni(II), S = 1] state. While Ni acts as a reversible spin switch, it is found that the electronic structure of the macrocycle backbone, where the frontier orbitals are mainly localized, remains unaffected. These findings pave the way for using the present porphyrin-based system as a platform for the realization of multifunctional devices where the magnetism and the optical/transport properties can be controlled simultaneously by independent stimuli

Electronic properties of the boroxine–gold interface: evidence of ultra-fast charge delocalization

We performed a combined experimental and theoretical study of the assembly of phenylboronic acid on the Au(111) surface, which is found to lead to the formation of triphenylboroxines by spontaneous condensation of trimers of molecules. The interface between the boroxine group and the gold surface has been characterized in terms of its electronic properties, revealing the existence of an ultra-fast charge delocalization channel in the proximity of the oxygen atoms of the heterocyclic group. More specifically, the DFT calculations show the presence of an unoccupied electronic state localized on both the oxygen atoms of the adsorbed triphenylboroxine and the gold atoms of the topmost layer. By means of resonant Auger electron spectroscopy, we demonstrate that this interface state represents an ultra-fast charge delocalization channel. Boroxine groups are among the most widely adopted building blocks in the synthesis of covalent organic frameworks on surfaces. Our findings indicate that such systems, typically employed as templates for the growth of organic films, can also act as active interlayers that provide an efficient electronic transport channel bridging the inorganic substrate and organic overlayer