Intramolecular Dipole Coupling and Depolarization in Self‐Assembled Monolayers

Quantum mechanical and classical atomistic computational methods are used to simulate the chain‐length dependence of depolarization effects in S(CH₂)_n?1CH₃ and S(CH₂)_n?1COOH self‐assembled monolayers on gold (111) surface. These calculations show that due to weak cooperative effects, the electrostatic properties of alkanethiol monolayers are well described by the gas phase dipole moments of the molecules. However, depolarization in monolayers with the molecules carrying head‐ and tail‐group dipoles, such as COOH‐terminated monolayers, strongly depends on the degree of intramolecular dipole coupling. Thus the electrostatic properties of self‐assembled monolayers can be engineered by changing the length of the aliphatic spacer between the polar groups. The transition from strong to weak coupling regime was found to be accompanied by the change in the sign of the asymptotic value of electrostatic potential above the surface of the monolayers and hence in the sign of the metal work function change. Therefore, the use of weakly polarizable spacers between the polar groups inside the molecules forming the SAM is beneficial for accessing a wider range of work‐function changes.     

A SAED and HREM study of structural defects in brownmillerite,LaBa(x)Sr(1-x)CuGaOy related oxides

The synthesis and microstructural characterization, by means of selected area electron diffraction (SAED) and high resolution electron microscopy (HREM), of the solid solution LaBa(x)Sr(1-x)CuGaO5 (0.1 < or = 5 x < or = 0.9) is reported. Although an average brownmillerite Ima2 structure is proposed for the whole compositional range, SAED and HREM clearly show that structural defects appear as barium content increases.     

Interaction of specialized cardiac conduction system with antiarrhythmic drugs: a simulation study

The use of antiarrhythmic drugs is common to treat heart rhythm disorders. Computational modeling and simulation are promising tools that could be used to investigate the effects of specific drugs on cardiac electrophysiology. In this paper, we study the multiscale effects of dofetilide, a drug that blocks IKr, from cellular to organ level paying special attention to its effect on heart structures, in particular the specialized cardiac conduction system (CCS). We include a model of the CCS in a patient-specific anatomical ventricular model and study the drug effects in simulations with and without a CCS. Results confirmed the expected effects of dofetilide at cellular level, increasing the action potential duration, and at organ level, prolonging the QT segment. Notable differences are shown between models with and without the CCS on action potential duration distributions. These techniques show the importance of heart heterogeneity and the global effects of the interaction of drugs with cardiac structures.     

Human-robot synchrony: flexible assistance using adaptive oscillators

We propose a novel method for movement assistance that is based on adaptive oscillators, i.e., mathematical tools that are capable of extracting the high-level features (amplitude, frequency, and offset) of a periodic signal. Such an oscillator acts like a filter on these features, but keeps its output in phase with respect to the input signal. Using a simple inverse model, we predicted the torque produced by human participants during rhythmic flexion-extension of the elbow. Feeding back a fraction of this estimated torque to the participant through an elbow exoskeleton, we were able to prove the assistance efficiency through a marked decrease of the biceps and triceps electromyography. Importantly, since the oscillator adapted to the movement imposed by the user, the method flexibly allowed us to change the movement pattern and was still efficient during the nonstationary epochs. This method holds promise for the development of new robot-assisted rehabilitation protocols because it does not require prespecifying a reference trajectory and does not require complex signal sensing or single-user calibration: the only signal that is measured is the position of the augmented joint. In this paper, we further demonstrate that this assistance was very intuitive for the participants who adapted almost instantaneously.     

Floral nectar phenolics as biochemical markers for the botanical origin of heather honey

In order to find out biochemical markers for the botanical origin of heather (Erica) honey, the phenolic metabolites present in heather floral nectar, collected from the honey-stomach of bees gathering nectar from these flowers, were analysed. The flavonoid fraction of nectar contained four main flavonoids. Two of them were quercetin and kaempferol 3-rhamnosides, and the other two were tentatively identified as myricetin 3-methyl ether and isorhamnetin 3-rhamnosides. Since the natural glycosides are hydrolysed by bee enzymes to render the corresponding aglycones, which are the metabolites detected in honey, acid hydrolysis of the nectar glycosides was achieved. The aglycones quercetin, myricetin 3-methyl ether, kaempferol and isorhamnetin were identified, as well as the gallic acid derivative ellagic acid. The analysis of Portuguese heather honey samples showed that ellagic acid was present in all the samples in significant amounts ranging between 100 g and 600 g per 100 g honey. The other nectar-derived flavonoids were also present, although some of them in very variable amounts. Ellagic acid and myricetin 3-methyl ether, which have not been detected in any of the monofloral honey samples investigated so far, with the only exception being a French honey sample of the botanically relatedCalluna (Ericaceae) which also contained ellagic acid, seem to be the most useful potential markers for the floral origin of heather honey. However, more detailed and extensive investigations are needed to prove the utility of these markers.     

Determination of fructose and glucose in cucurbitaceae by h.p.l.c.

High performance liquid chromatography (h.p.l.c.) was used to characterise and quantify fructose and glucose in seven members of the Cucurbitaceae family. The h.p.l.c. system consisted of a μ-Bondapak/Carbohydrate packed column, a solvent system of acetonitrile-water (800 ml l^?-1) with a flow rate of 2.5 ml min^?-1, and a refractive index detector. The analysis, including sample preparation, was completed in less than 45 min. The quantities of fructose and glucose obtained were, except for one sample, <1% on a fresh weight basis, and the glucose: fructose ratios ranged from 0.41:1 to 0.93:1.     

News: United Kingdom to set air quality emission standards

Government.     

Organic field-effect transistors as new paradigm for large-area molecular junctions

Self-Assembly Monolayers (SAMs) are considered a promising route for solving technological hindrances (such as bias-stress, contact resistance, charge trapping) affecting the electrical performances of the Organic Field-Effect Transistors (OFETs). Here we use an OFET based on pentacene thin film to investigate the charge transport across conjugated SAMs at the Au/pentacene interface. We synthesized a homolog series of π-conjugated molecules, termed Tn-C8-SH, consisting of a n-unit oligothienyl Tn (n = 1…4) bound to an octane-1-thiol (C8-SH) chain that self-assembles on the Au electrodes. The multi-parametric response of such devices yields an exponential behavior of the field-effect mobility (μ), current density (J), and total resistivity (R), due to the SAM at the charge injection interface (i.e. Au-SAM-pentacene). The surface treatment of the OFETs induces a clear stabilization of different parameters, like sub-threshold slope and threshold voltage, thanks to standardized steps in the fabrication process.     

Hybrid Organic/Inorganic Nanostructures for Highly Sensitive Photoelectrochemical Detection of Dissolved Oxygen in Aqueous Media

Precise, reliable, and remote measurement of dissolved oxygen in aqueous media is of great importance for many industrial, environmental, and biological applications. In particular, photoelectrochemical sensors working in differential mode have recently demonstrated promising properties, in terms of stability, sensitivity, and application potential. Here, a new approach is presented, combining visible light sensitivity, efficient photocurrent generation, and solution‐processed fabrication methods of conjugated polymers, with charge carriers selectivity, energetic alignment favorable to efficient interfacial charge transfer and high surface area achievable by using metal oxide nanostructures. Extensive characterization and optimization of the hybrid organic/inorganic system are carried out, leading to the realization of an oxygen sensor device, based on nanostructured palladium oxide/poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole]/[6,6]phenyl‐C61‐butyric acid methyl ester (PdO/APFO‐3:PCBM) as materials of choice. State‐of‐the‐art sensitivity, amounting at ?5.87 μA cm^?2 ppm^?1, low background signal, in the order of ?4.85 μA cm^?2, good electrochemical stability for more than 2 h of continuous functioning and high reproducibility of the signal over the pH 1 to 10 range, are reported, making the hybrid device suitable for several practical uses. The results fully validate the mixed organic/inorganic approach for photoelectrochemical applications, and pave the way for its further exploitation in fields like waste water treatment, environmental monitoring, and water splitting.