Notes

[Mesenteric panniculitis since the initial symbol of an a cellular lymphoma].
The latter limitation is likely to apply to all molecular rotors.Through first-principles calculations, the electron-phonon scattering of two-dimensional monolayer AsSb is investigated. The Boltzmann transport equation is used to compute the phonon limited carrier mobility. We find that the optical phonon scattering rates are much larger than acoustic ones around the valence band maximum (VBM) and the conduction band minimum (CBM). The phonon-decomposed scattering results show that transverse optical (TO) phonon modes dominate the scattering around VBM, while longitudinal and out-of-plane acoustic modes contribute mostly to the scattering at higher energy. TO phonon modes dominate the scattering for electrons over all energy level, and the electron-phonon matrix element analysis verified the results. Finally, we observed that the largest mean free paths for hot holes and hot electrons are 20 nm and 8 nm, respectively. That is the best range to extract the hot holes and hot electrons. More interestingly, owing to the in-pane net dipole moment of AsSb, the intrinsic electron/hole mobility of AsSb are 38/50 cm2 V-1 s-1, which are less than monolayer arsenene and antimonene.This paper presents a grand canonical formalism to treat electrochemical effects at interfaces. This general formalism is linked with the classical chemical hydrogen electrode (CHE) approximation and an improved approximation is proposed. This new approximation including a higher order correction that (i) keeps the low computational cost of classical CHE approach, (ii) does not require to know the type of reaction (electrochemical/not electrochemical) and (iii) should give better estimates in many problematic cases. Beyond the applicability domain of this new approximation, the homogeneous background method (HBM) which is a potential dependent density functional theory method is then presented. HBM allows computing and extracting, at ab initio level, electrochemical properties of molecules either adsorbed or in the double layer. In particular, quantitative redox potential and number of exchanged electrons can be computed giving access to non-integer electron exchange or decoupled electron/proton transfer reactions. Tools for rationalizing electrochemical reactivity consisting of potential dependant projected density of states, Fukui function and metallicity index are defined. The methodology and tools are applied to examples relevant to the energy domain in order the compare reactivity in the outer Helmholtz plane and at the surface. Then, the combination of HBM and reactivity create a toolbox usable to predict and investigate the different redox, degradation and ageing processes occurring at an electrochemical interface such as the one found in energy materials but also in all electrochemical applications.Hysteresis in the current response to a varying gate voltage is a common spurious effect in carbon-based field effect transistors. Here, we use electric transport measurements to probe the charge transport in networks of armchair graphene nanoribbons with a width of either 5 or 9 carbon atoms, synthesized in a bottom-up approach using chemical vapor deposition. Our systematic study on the hysteresis of such graphene nanoribbon transistors, in conjunction with temperature-dependent transport measurements shows that the hysteresis can be fully accounted for by trapping/detrapping carriers in the SiO2 layer. We extract the trap densities and depth, allowing us to identify shallow traps as the main origin of the hysteresis effect.We investigate the effect of pressure, temperature and acidity on the composition of water-rich carbon-bearing fluids under thermodynamic conditions that correspond to the Earth's deep crust and upper mantle. Our first-principles molecular dynamics simulations provide mechanistic insight into the hydration shell of carbon dioxide, bicarbonate and carbonate ions, and into the pathways of the acid/base reactions that convert these carbon species into one another in aqueous solutions. At temperatures of 1000 K and higher, our simulations can sample the chemical equilibrium of these acid/base reactions, thus allowing us to estimate the chemical composition of diluted carbon dioxide and (bi)carbonate ions as a function of acidity and thermodynamic conditions. We find that, especially at the highest temperature, the acidity of the solution is essential to determine the stability domain of CO2 vs. HCO3- vs. CO32-.The reactions of SiHPh(NCH2PPh2)2C6H4-1,2 with a range of zerovalent group 10 reagents afford the homoleptic bimetallic complexes [M2μ-κ3-Si,P,P'-SiPh(CH2PPh2)2C6H42] (M = Ni, Pd, Pt) in which the M-M bond is unsymmetrically bridged by two σ-silyl groups. The asymmetry of the M2Si2 core increases from Ni through Pd to Pt and is consistent with a bonding description in which one metal acts as an electron pair donor to a trigonal bipyramidal 'Z-type' silicon centre, reminsicent of semi-bridging coordination by CO, carbynes and boryl ligands.The synthesis and characterization of a series of N-heterocyclic carbene (NHC) complexes of Au(iii), (NHC)AuCl3, is described. High yields are obtained when the corresponding Au(i) species (NHC)AuCl are oxidized with inexpensive aqua regia. The oxidation is in some cases accompanied by substitution and/or anti addition of Cl2 across the backbone C[double bond, length as m-dash]C bond of unsaturated NHC ligands.Molecular conformation is closely related to the functional properties of macromolecules. In order to prove that the bioactivity of mulberry fruit polysaccharides (MFPs) is greatly affected by the conformation, and to improve adsorption properties, we have designed Fe3O4@MFPNPs core-shell nanoparticles. The spherical Fe3O4@MFPNPs have been successfully synthesized with particle size distribution in the ranges of 3-10 nm and 68-164 nm, which are smaller than their previously prepared original polysaccharides and MFP-Fe(iii). The Fe3O4@MFPNPs showed better antioxidant activity in comparison to MFP and MFP-Fe(iii). The difference in the antioxidant activity between Fe3O4@MFPNPs and MFP-Fe(iii), both of which were modified based on elemental iron, may be attributed to their different conformations MFP-Fe(iii) were rod-shaped, while Fe3O4@MFPNPs were spherical. Furthermore, Fe3O4@MFPNPs also exhibited greater absorption in the small intestine, which can promote its application in human health.Two-dimensional materials such as graphene (G) and hexagonal boron nitride (BN) have demonstrated potential applications in membrane science and in particular for the harvesting of blue energy. Although pure G and BN atomic layers are known to remain inert towards neutral water, one may wonder about the aqueous reactivity of hybridized monolayers formed by joining BN and G sheets in a planar fashion. Here, we perform ab initio molecular dynamics calculations of liquid water in contact with all possible planar heterostructures. Remarkably, we could observe the spontaneous chemisorption and dissociation of the interfacial water molecule into its self-ions at one specific and non-standard one-dimensional border. Our simulations predict that this type of heterostructure is prone to ionize liquid water in the absence of any electrical gating.DFT-based molecular dynamics simulations of the electrified air-liquid water interface are presented, where a homogeneous field is applied parallel to the surface plane. We unveil the field intensity for the onset of proton transfer and molecular dissociation; the protonic current/proton conductivity is measured as a function of the field intensity/voltage. The air-water interface is shown to exhibit a proton conductivity twice the one in the liquid water for field intensities below 0.40 V Å-1. We show that this difference arises from the very specific organization of water in the binding interfacial layer (BIL, i.e. the air-water interface region) into a 2D-HBond-network that is maintained and enforced at the electrified interface. Beyond fields of 0.40 V Å-1, water in the BIL and in the bulk liquid are aligned in the same way by the rather intense fields, hence leading to the same proton conductivity in both BIL and bulk water.Four trinuclear ruthenium carbonyl clusters, (6-BrPyCHRO)2Ru3(CO)8 (R = 4-OCH3C6H4, 1a; R = 4-BrC6H4, 1b) and (2-OC6H4-HC[double bond, length as m-dash]N-C6H4R)2Ru3(CO)8 (R = 4-OCH3, 2a; R = 4-Br, 2b), were synthesized from the reactions of Ru3(CO)12 with the corresponding N,O-bidentate ligands (two pyridyl alcohols and two Schiff bases) respectively in a ratio of 1  2. Three new complexes 1b, 2a and 2b have been fully characterized by elemental analysis, FT-IR, NMR and X-ray crystallography. The catalytic activity of these ruthenium complexes for the aerobic oxidation of primary benzylic amines to amides and nitriles in the presence of t-BuOK was investigated, of which the Schiff base complex 2a was found to exhibit the highest activity.An understanding of the interaction of water with perovskite is crucial in improving the structural stability of the perovskite. Hence, in this study, the structural and electronic properties of the γ-CsPbI3(220) perovskite surface upon the adsorption of water molecules have been investigated based on density functional theory calculations. Also, we perform first-principles ab initio molecular dynamics simulations (AIMD) to explore the structural stability of the γ-CsPbI3(220) perovskite surface in the presence of water molecules, and the results are compared with the conventional cubic CH3NH3PbI3(100) perovskite surface. The water molecules show stronger interactions with the (220) surface of γ-CsPbI3 than the (100) surface of CH3NH3PbI3. However, AIMD results demonstrate that the former is much more stable, and no trace of surface degradation was observed upon the adsorption of water molecules.2D extended organic cocrystals were constructed using 1,4-diiodotetrafluorobenzene and aromatic aldehydes via IOaldehyde halogen bonds on an Au(111) surface. SU11274 chemical structure The competition and synergy of halogen bonds and hydrogen bonds in 2D co-crystallization were revealed by scanning tunneling microscopy.Twenty clusters of the general formula [(μ-H)2Ru3(μ3-S)(CO)7(μ-P-P*)] (P-P* = chiral diphosphine of the ferrocene-based Walphos or Josiphos families) have been synthesised and characterised. The clusters have been tested as catalysts for asymmetric hydrogenation of tiglic acid [trans-2-methyl-2-butenoic acid]. The observed enantioselectivities and conversion rates strongly support catalysis by intact Ru3 clusters. A catalytic mechanism involving an active Ru3 catalyst generated by CO loss from [(μ-H)2Ru3(μ3-S)(CO)7(μ-P-P*)] has been investigated by DFT calculations.Artificial photosynthesis by a semiconductor-oxide-based photocatalysis is presently challenging due to low CO2 conversion rates and poor product selectivity. To promote CO2 reduction, Pt/TiO2 has been deemed as a classic photocatalyst. In this study, we restudy Pt/TiO2 for the thermally assisted photocatalytic reduction of CO2 and reveal a different story between photocatalysis and photothermal catalysis. For example, when using disordered Pt/TiO2-x, the CO2 conversion via photocatalysis at 298 K is not impressive. However, when the system temperature is increased to 393 K, the CO2 conversion rate is significantly enhanced by a factor of 155 as compared to that obtainable from pristine TiO2; further, surprisingly high selectivity of CH4 (87.5%) could be achieved. Thermally coupled photocatalysis yields the enhanced evolution of H2 side products over Pt (4.06 nm)/TiO2 and promoted H2 splitting over Pt (2.33 nm)/TiO2, which is seldom observed in conventional Pt/TiO2 photocatalysis. The synergy of improved charge separation at the Pt/TiO2-x interface induced by surface disordering and accelerated H2 consumption near smaller Pt nanoparticles by thermal assistance are believed to be critically important for the simultaneous enhancement of CO2 conversion rates and CH4 product selectivity.
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