A new approach to local hardness

The applicability of the local hardness as defined by the derivative of the chemical potential with respect to the electron density is undermined by an essential ambiguity arising from this definition. Further, the local quantity defined in this way does not integrate to the (global) hardness - in contrast with the local softness, which integrates to the softness. It has also been shown recently that with the conventional formulae, the largest values of local hardness do not necessarily correspond to the hardest regions of a molecule. Here, in an attempt to fix these drawbacks, we propose a new approach to define and evaluate the local hardness. We define a local chemical potential, utilizing the fact that the chemical potential emerges as the additive constant term in the number-conserving functional derivative of the energy density functional. Then, differentiation of this local chemical potential with respect to the number of electrons leads to a local hardness that integrates to the hardness, and possesses a favourable property; namely, within any given electron system, it is in a local inverse relation with the Fukui function, which is known to be a proper indicator of local softness in the case of soft systems. Numerical tests for a few selected molecules and a detailed analysis, comparing the new definition of local hardness with the previous ones, show promising results.Comment: 30 pages (including 6 figures, 1 table

Tuning crystal ordering, electronic structure, and morphology in organic semiconductors: Tetrathiafulvalenes as a model case

Tetrathiafulvalenes (TTFs) are an appealing class of organic small molecules giving rise to some of the highest performing active materials reported for organic field effect transistors (OFETs). Because they can be easily chemically modified, TTF-derivatives are ideal candidates to perform molecule-property correlation studies and, especially, to elucidate the impact of molecular and crystal engineering on device performance. A brief introduction into the state-of-the-art of the field-effect mobility values achieved with TTF derivatives employing different fabrication techniques is provided. Following, structure-performance relationships are discussed, including polymorphism, a phenomenon which is crucial to control for ensuring device reproducibility. It is also shown that chemical modification of TTFs has a strong influence on the electronic structure of these materials, affecting their stability as well as the nature of the generated charge carriers, leading to devices with p-channel, n-channel, or even ambipolar behaviour. TTFs have also shown promise in other applications, such as phototransistors, sensors, or as dopants or components of organic metal charge transfer salts used as source-drain contacts. Overall, TTFs are appealing building blocks in organic electronics, not only because they can be tailored to perform fundamental studies, but also because they offer a wide spectrum of potential applications. Tetrathiafulvalenes are promising active materials in organic field-effect transistors (OFETs), in which they exhibit high performances. An overview is provided of the use of this family of materials as a model building block for OFETs to highlight general concepts of organic semiconductors and their use in devices.The authors thank the ERC StG 2012-306826 e-GAMES project, the Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), the DGI (Spain) with projects BE-WELL CTQ2013-40480-R and MAT2012-30924, and the Generalitat de Catalunya (2014-SGR-17, 2014SGR97 and XRQTC).Peer Reviewe

Understanding the Effects of a Tannin Extract on Forage Protein Digestion in the Rumen and Abomasum Using a Dynamic Artificial Digestive System Coupled to a Digestomic Approach

Improving the use efficiency of dietary protein in ruminants is a major challenge to decrease feed supplementation and significantly decrease nitrogen (N) losses to the environment. The aim of this study was to characterize the effects of tannins on protein digestion in the rumen and in conditions simulating the abomasum, using a dynamic in vitro digestive system coupled to a digestomic approach. Three ruminally-cannulated sheep fed with alfalfa hay were infused daily with a solution of tannins, while three other sheep were infused with water (control). Standardized ruminal fluid was introduced into the digester, which simulated the transit of digesta under physicochemical conditions mimicking the abomasum in terms of pH regulation, digestive enzyme infusions and transit rate. Protein degradation in the rumen and in the simulated abomasum was analyzed by determination of fermentation end-products, and identification and quantification of peptides (Label Free Quantification) by LC-MS/MS high resolution (Orbitrap). The analysis of rumen samples showed that tannins result in a clear decrease of fermentation end-products related to protein degradation, namely ammonia (NH3) and iso-volatile fatty acids (VFA), and a greater abundance of the Rubisco, a major plant protein. In the simulated abomasal compartment, the peptidomic analysis showed that the hydrolysis intensity of Rubisco was higher in the presence of tannins compared to the control group. These results indicate that protein-tannin complexes could be dissociated in the physico-chemical conditions of the abomasum, increasing the flow of peptides to the intestine after protection of protein by tannins in the rumen

Probing molecular arrangements of the organic semiconductor 2,7-Dioctyl[1]benzothieno[3,2- b][1]benzothiophene thin film at the interface by UV Resonant Raman scattering

Raman spectroscopy was employed to investigate nanometric thick films of the organic semiconductor 2,7-Dioctyl[1]benzothieno[3,2-b][1]benzothiophene, following a comprehensive vibrational characterization of the compound condensed phases at various excitation wavelengths. UV Raman excitation enabled the characterization of the thin films, revealing that the molecular orientation at the film/air interface is characterized by a different organization and/or a high degree of disorder compared to the bulk phase. The low penetration depth of the UV Raman excitation allows for the retrieval of this information, unlike the XRD data

Manipulating the fluorescence lifetime at the sub-cellular scale via photo-switchable barcoding

Fluorescent barcoding is a pivotal technique for the investigation of the microscale world, from information storage to the monitoring of dynamic biochemical processes. Using fluorescence lifetime as the readout modality offers more reproducible and quantitative outputs compared to conventional fluorescent barcoding, being independent of sample concentration and measurement methods. However, the use of fluorescence lifetime in this area has been limited by the lack of strategies that provide spatiotemporal manipulation of the coding process. In this study, we design a two-component photo-switchable nanogel that exhibits variable fluorescence lifetime upon photoisomerization-induced energy transfer processes through light irradiation. This remotely manipulated fluorescence lifetime property could be visually mapped using fluorescence lifetime imaging microscopy (FLIM), allowing selective storage and display of information at the microscale. Most importantly, the reversibility of this system further provides a strategy for minimizing the background influence in fluorescence lifetime imaging of live cells and sub-cellular organelles. Using fluorescence lifetime as the readout modality offers more reproducible and quantitative outputs compared to conventional fluorescent barcoding, being independent of sample concentration and measurement methods. Here, the authors design a photo-switchable nanogel exhibiting variable fluorescence lifetime, and demonstrate visual mapping by using fluorescence lifetime imaging microscopy on a sub-cellular scale.This work was supported by the ERC (grant number 615142), EPSRC, and the University of Birmingham, the Ministerio de Economia y Competitividad (MINECO) of Spain (project CTQ2016-80375-P) and the Basque Government (grant IT-324-07). The authors acknowledge the computational and technical and human support provided by DIPC. Y.X. acknowledges Chancellor's International Scholarship (University ofWarwick) for funding. All three reviewers are thanked for their time and contribution to the final version of this paper

Dynamics of modal power distribution in a multimode semiconductor laser with optical feedback

The dynamics of power distribution between longitudinal modes of a multimode semiconductor laser subjected to external optical feedback is experimentally analyzed in the low-frequency fluctuation regime. Power dropouts in the total light intensity are invariably accompanied by sudden activations of several longitudinal modes. These activations are seen not to be simultaneous to the dropouts, but to occur after them. The phenomenon is statistically analysed in a systematic way, and the corresponding delay is estimated.Comment: 3 pages, 4 figures, revte

Optical signature of symmetry variations and spin-valley coupling in atomically thin tungsten dichalcogenides

Motivated by the triumph and limitation of graphene for electronic applications, atomically thin layers of group VI transition metal dichalcogenides are attracting extensive interest as a class of graphene-like semiconductors with a desired band-gap in the visible frequency range. The monolayers feature a valence band spin splitting with opposite sign in the two valleys located at corners of 1st Brillouin zone. This spin-valley coupling, particularly pronounced in tungsten dichalcogenides, can benefit potential spintronics and valleytronics with the important consequences of spin-valley interplay and the suppression of spin and valley relaxations. Here we report the first optical studies of WS2 and WSe2 monolayers and multilayers. The efficiency of second harmonic generation shows a dramatic even-odd oscillation with the number of layers, consistent with the presence (absence) of inversion symmetry in even-layer (odd-layer). Photoluminescence (PL) measurements show the crossover from an indirect band gap semiconductor at mutilayers to a direct-gap one at monolayers. The PL spectra and first-principle calculations consistently reveal a spin-valley coupling of 0.4 eV which suppresses interlayer hopping and manifests as a thickness independent splitting pattern at valence band edge near K points. This giant spin-valley coupling, together with the valley dependent physical properties, may lead to rich possibilities for manipulating spin and valley degrees of freedom in these atomically thin 2D materials

Three-dimension structure of ventricular myocardial fibers after myocardial infarction

<p>Abstract</p> <p>Background</p> <p>To explore the pathological changes of three-dimension structure of ventricular myocardial fibers after anterior myocardial infarction in dog heart.</p> <p>Methods</p> <p>Fourteen acute anterior myocardial infarction models were made from healthy dogs (mean weight 17.6 ± 2.5 kg). Six out of 14 dogs with old myocardial infarction were sacrificed, and their hearts were harvested after they survived the acute anterior myocardial infarction for 3 months. Each heart was dissected into ventricular myocardial band (VMB), morphological characters in infarction region were observed, and infarct size percents in descending segment and ascending segment were calculated.</p> <p>Results</p> <p>Six dog hearts were successfully dissected into VMB. Uncorresponding damages in myocardial fibers of descending segment and ascending segment were found in apical circle in anterior wall infarction. Infarct size percent in the ascending segment was significantly larger than that in the descending segment (23.36 ± 3.15 (SD) vs 30.69 ± 2.40%, P = 0.0033); the long axis of infarction area was perpendicular to the orientation of myocardial fibers in ascending segment; however, the long axis of the infarction area was parallel with the orientation of myocardial fibers in descending segment.</p> <p>Conclusions</p> <p>We found that damages were different in both morphology and size in ascending segment and descending segment in heart with myocardial infarction. This may provide an important insight for us to understand the mechanism of heart failure following coronary artery diseases.</p

Assessment of the relationship between the upper and lower arch changes with the opening of the expanding screw after the rapid maxillary expansion

Objective: the purpose of this study is to assess the relationship of the upper and lower arch dimension changes after the rapid maxillary expansion (RME) with the screw opening of the modified Hyrax® type appliance. Materials and methods: initial (T1) and final (T2) models of study of 63 children between 7 years and 6 months and 16 years and 5 months were performed. From these, 21 showed maxillary atresia and/ or posterior crossbite and were submitted to expansion and 42 children formed the control group .The appliance used in this work was the modified Hyrax appliance using the 7mm expanding screws 'Dentarum'. The measures of the upper intercanine and the upper and lower intermolar distances were performed in plaster models with the help of a digital paquimeter. The opening of the appliance's screw was also assessed. Results: the RME provoked a statistically significant increase in the upper interdental distances and no statistic significance in the lower interdental distances, i.e. the change in the 16 - 26, 13 - 23 and 36 - 46 distance was of 5,85 mm, 5,31 and 0,34 mm respectively. The average opening of the expander screw, which was of 6,27 mm. Conclusion: the appliance's opening is related to the interdental distance changes, i.e. for each appliance's opening mm, a 0,94 variation in the upper intermolar distance, a 0,87 in the upper intercanine distance and 0,054 in the lower intermolar distance are provoked