Probing Intermolecular H-Bonding Interactions in Cyanuric Acid Networks: Quenching of the N K-Edge Sigma Resonances

The electronic characterization of the cyanuric acid both in gas phase and when embedded within an H-bonded scheme forming a monolayer on the Au(111) surface has been performed by means of X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The experimental spectra at the N, O, and C K-edges have been assigned with the support of DFT calculations, and the combination between theory and experiment has allowed to us investigate the effect of the H-bonding intermolecular interaction on the spectra. In particular, the H-bond formation in the monolayer leads to a quenching of the N 1s NEXAFS resonances associated with transitions to the sigma empty orbitals localized on the N-H portion of the imide group. On the other hand, the pi* empty states remain substantially unperturbed. From a computational point of view, it has been shown that the DFT-TP scheme is not able to describe the N 1s NEXAFS spectra of these systems, and the configuration mixing has to be included, through the TDDFT approach in conjunction with the range-separated XC CAM-B3LYP functional, to obtain a correct reproduction of the N 1s core spectra

Inhomogeneous charge transfer within monolayer zinc phthalocyanine absorbed on TiO2(110)

The d-orbital contribution from the transition metal centers of phthalocyanine brings difficulties to understand the role of the organic ligands and their molecular frontier orbitals when it adsorbs on oxide surfaces. Here we use zinc phthalocyanine (ZnPc)TiO (110) as a model system where the zinc d-orbitals are located deep below the organic orbitals leaving room for a detailed study of the interaction between the organic ligand and the substrate. A charge depletion from the highest occupied molecular orbital is observed, and a consequent shift of N1s and C1s to higher binding energy in photoelectron spectroscopy (PES). A detailed comparison of peak shifts in PES and near-edge X-ray absorption fine structure spectroscopy illustrates a slightly uneven charge distribution within the molecular plane and an inhomogeneous charge transfer screening between the center and periphery of the organic ligand: faster in the periphery and slower at the center, which is different from other metal phthalocyanine, e.g., FePcTiO . Our results indicate that the metal center can substantially influence the electronic properties of the organic ligand at the interface by introducing an additional charge transfer channel to the inner molecular part

High resolution NEXAFS of perylene and PTCDI : a surface science approach to molecular orbital analysis

We made use of synchrotron radiation to perform near edge X-ray absorption fine structure spectroscopy, NEXAFS, at the carbon K-edge of perylene and perylene-tetracarboxylic-diimide, PTCDI. Reference spectra measured for isolated molecules in the gas phase are compared with polarization dependent NEXAFS spectra measured on highly oriented thin films in order to study the symmetry of the molecular orbitals. The molecular overlayers are grown onto the rutile TiO2(110) surface for which the large anisotropic corrugation effectively drives the molecular orientation, while its dielectric nature prevents the rehybridization of the molecular orbitals. We employed density functional theory, DFT, calculations to disentangle the contribution of specific carbon atoms to the molecular density of states. Numerical simulations correctly predict the observed NEXAFS azimuthal dichroism of the \u3c3* resonances above the ionization threshold, from which we determine the full geometric orientation of the overlayer molecules. A discrepancy observed for the spectral contribution of the imide carbon atom to the calculated unoccupied molecular orbitals has been explained in terms of initial state effects, as determined by Hartree-Fock corrections and in full agreement with the corresponding shift of the C 1s core level measured by X-ray photoelectron spectroscopy, XPS. \ua9 the Partner Organisations 2014

m-MTDATA on Au(111): Spectroscopic Evidence of Molecule-Substrate Interactions

The starburst π-conjugated molecule based on triphenylamine (TPA) building blocks, 4,4′,4″-tris(N-3-ethylphenyl-N-phenylamino)triphenylamine (C57H48N4, m-MTDATA), is widely used in optoelectronic devices due to its electron-donating properties. The electronic structure of m-MTDATA adsorbed on an Au(111) surface was investigated by means of photoelectron spectroscopy (PES) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results were further compared to gas-phase measurements and DFT calculations. Our results clearly indicate a significant molecule-substrate interaction that induces considerable modifications on the electronic structure of the adsorbate compared to the isolated molecule. The energy level alignment analysis shows that the HOMO-LUMO gap is filled by new interface states

"Active surfaces" as Possible Functional Systems in Detection and Chemical (Bio) Reactivity

This article presents design strategies to demonstrate approaches to generate functionalized surfaces which have the potential for application in molecular systems; sensing and chemical reactivity applications are exemplified. Some applications are proven, while others are still under active investigation. Adaptation and extension of our strategies will lead to interfacing of different type of surfaces, specific interactions at a molecular level, and possible exchange of signals/cargoes between them. Optimization of the present approaches from each of five research groups within the NCCR will be directed towards expanding the types of functional surfaces and the properties that they exhibit

E-grocery challenges and remedies: Global market leaders perspective

The purpose of the study is to identify logistic elements germane to e-grocery businesses, and to reveal the challenges collateral with each logistic element. Further, it strives to create a better understanding of specific remedies that have been employed by top e-grocery retailers to overcome existing challenges while aligning identified challenges with Turban’s framework. Extensive semi-structured interviews were conducted with management staff in three of the top ten global online grocery retailers and another that was a market leader in a European country. The qualitative data collected was transcribed and coded using a non-hierarchical axial coding to identify emerging themes in content analysis. The results expose a range of challenges that could be compartmentalised into three broad categories, in harmony with the different stages of the order fulfilment process. Interestingly, the study found that most challenges were operational rather than tactical or strategic in nature. While the study expands existing knowledge, its revelation that most challenges lie in the management of roles and responsibilities domain is instructive. This makes it imperative for practitioners to focus on this specific area if meaningful improvement in e-grocery retailing performance is to be realised. This research offers a systematic understanding of supply and distribution challenges, including remedies utilised to ameliorate the effect of the challenges from the perspectives of the top companies in the industry. These remedies can be invaluable for existing and emerging e-grocers

A new field in monkey's frontal cortex: premotor ear-eye field (PEEF)

In macaque monkey, area 8B is cytoarchitectonically considered a transitional area between the granular Brodmann area 9, rostrally, and the rostral part of the dorsal agranular Brodmann area 6, caudally. As for electrophysiological data, microstimulation of area 8B evokes ear and/or eye movements; unit activity recording shows neurons encoding different auditory environmental stimuli and ear and/or eye movements. Moreover, visual attentive fixation modulates the discharge of auditory environmental neurons and auditory-motor neurons. As for anatomical data, area 8B is connected with auditory cortical areas, superior colliculus and cerebellum. Current functional and anatomical evidences support that area 8B is a specific Premotor Ear-Eye Field (PEEF) involved in auditory stimuli recognition and in orienting processes. In conclusion, we suggest that PEEF could play an important role in engaging the auditory spatial attention for the purpose of orienting eye and ear towards the sound source

Orienting movements in area 9 identified by long-train ICMS

The effect of intracortical microstimulation has been studied in several cortical areas from motor to sensory areas. The frontal pole has received particular attention, and several microstimulation studies have been conducted in the frontal eye field, supplementary eye field, and the premotor ear-eye field, but no microstimulation studies concerning area 9 are currently available in the literature. In the present study, to fill up this gap, electrical microstimulation was applied to area 9 in two macaque monkeys using long-train pulses of 500-700-800 and 1,000 ms, during two different experimental conditions: a spontaneous condition, while the animals were not actively fixating on a visual target, and during a visual fixation task. In these experiments, we identified backward ear movements, goal-directed eye movements, and the development of head forces. Kinematic parameters for ear and eye movements overlapped in the spontaneous condition, but they were different during the visual fixation task. In this condition, ear and eye kinematics have an opposite behavior: movement amplitude, duration, and maximal and mean velocities increase during a visual fixation task for the ear, while they decrease for the eye. Therefore, a top-down visual attention engagement could modify the kinematic parameters for these two effectors. Stimulation with the longest train durations, i.e., 800/1,000 ms, evokes not only the highest eye amplitude, but also a significant development of head forces. In this research article, we propose a new vision of the frontal oculomotor fields, speculating a role for area 9 in the control of goal-directed orienting behaviors and gaze shift control

Essential oil metabolites can regulate adrenal androgen production by inhibition of CYP17A1 activities.

Endocrine-disrupting chemicals (EDCs) can affect human steroid metabolism. Previous clinical case reports have shown that some Essential Oils (EOs) like lavender oil and tea tree oil may act as potential EDCs and are linked to prepubertal gynecomastia in boys and premature thelarche in girls due to regular exposure to lavender based fragrances among Hispanic population. These studies suggested role of EOs in steroid metabolism in humans. We have screened a range of EO metabolites for effects on androgen production by CYP17A1. For preliminary screening, human adrenal NCI H295R cells were treated with 10 µM of test compounds for 24 hours. The test compounds had been extracted and purified from natural resources and are found as major components in EOs. For CYP17A1 activity, the conversion of radiolabelled substrate, 17-Hydroxy-pregnenolone to Dehydroepiandrosterone was determined using tritiated water release assay. Eucalyptol, Dihydro-β-Ionone, (-)-α-pinene were extracted from eucalyptus, rose and pine resin. Out of about 50 test compounds, eucalyptol, Dihydro-β-Ionone & (-)-α-pinene showed 20% to 40% inhibition of DHEA production. Rest of the compounds showed either no or low inhibition. Some compounds were also tested for effects on CYP19A1 (aromatase) activity where upto 30% inhibition was observed. EOs are often used in various beauty and hygiene products as they have few known side-effects. However, prolonged exposure to these products may result in steroid imbalance. Due to their anti-androgenic activity, these compounds should be studied further as chemical leads for the treatment of hyperandrogenic disorders such as Prostate cancer and Polycystic ovary syndrome

Facial Muscle Coordination in Monkeys during Rhythmic Facial Expressions and Ingestive Movements

Evolutionary hypotheses regarding the origins of communication signals generally, and primate orofacial communication signals in particular, suggest that these signals derive by ritualization of noncommunicative behaviors, notably including ingestive behaviors such as chewing and nursing. These theories are appealing in part because of the prominent periodicities in both types of behavior. Despite their intuitive appeal, however, there are little or no data with which to evaluate these theories because the coordination of muscles innervated by the facial nucleus has not been carefully compared between communicative and ingestive movements. Such data are especially crucial for reconciling neurophysiological assumptions regarding facial motor control in communication and ingestion. We here address this gap by contrasting the coordination of facial muscles during different types of rhythmic orofacial behavior in macaque monkeys, finding that the perioral muscles innervated by the facial nucleus are rhythmically coordinated during lipsmacks and that this coordination appears distinct from that observed during ingestion