Tuning crystal structure of iridium-incorporated titanium dioxide nanosupport and its influence on platinum catalytic performance in direct ethanol fuel cells

Titanium dioxide (TiO₂) has recently been used as a promising support for platinum (Pt)-based catalysts; however, its very low electrical conductivity and understanding the effect of the TiO₂ structure on Pt electrocatalytic performance for ethanol electro-oxidation reaction (EOR) are major challenges in direct ethanol fuel cells. This study reports an easy and green approach to control the crystal structures of a robust iridium-incorporated TiO₂ nanomaterial and its effect on the Pt electrocatalytic performance for EOR. A green hydrothermal route is used to fabricate iridium-modified TiO₂ nanosupports with different structures by controlling the reaction temperature and time as well as solution pH without using further calcination, followed by the anchoring of Pt nanoparticles (NPs) via a surfactant-free modified reduction route. The experimental results indicate that the pure structure of the iridium-modified TiO₂ nanosupport can easily be obtained by controlling the solution pH. In terms of EOR, all prepared catalysts show more effective performance than the commercial Pt/C catalyst. Among the prepared catalysts, the Pt anchored on the rutile iridium-incorporated TiO₂ exhibits higher EOR performance than on the anatase iridium-incorporated TiO₂ nanosupport, with negative onset potential, high current density, and electrochemical stability. The enhancement is assigned to the great adsorption and desorption ability as well as the high natural resistance to metal NPs ripening on (110) facets of the rutile structure compared with the (101) facets of the anatase structure. This exploration can offer an efficient route for tuning the structure of metal oxides and understanding the effect of the structure of the TiO₂-based support on the Pt catalytic performance.     

Injective modules and torsion functors*

A commutative ring is said to have ITI with respect to an ideal 𝔞 if the 𝔞-torsion functor preserves injectivity of modules. Classes of rings with ITI or without ITI with respect to certain sets of ideals are identified. Behavior of ITI under formation of rings of fractions, tensor products, and idealization is studied. Applications to local cohomology over non-noetherian rings are given.     

Nonlinear vibration response of shear deformable FGM sandwich toroidal shell segments

Meccanica - The nonlinear vibration investigation of toroidal shell segment (TSS) with an analytical approach is presented in this paper. The TSS is considered as a sandwich structure with FGM core...     

An Upper Bound Kinematic Approach to the Shakedown Analysis of Structures

A reduced but equivalent form of Koiter's upper bound kinematic theorem, which does not involve time integrals, is deduced, provided that the plastic strain rates at every point of a structure are confined to a certain number of possible directions in the strain space. Generally it yields an upper bound on the shakedown factor, which improves upon the previous one by Pham and Stumpf.Sommario. Una forma ridotta ma equivalente del teorema cinematica di Koiter sul limite superiore, che non coinvolge integrali temporali, viene dedotta sotto la condizione che le velocità di deformazione plastica in ogni punto della struttura siano confinate ad un certo numero di possibili direzioni nello spazio delle deformazioni. Generalmente, ciò produce un limite superiore sul fattore di shakedown, che migliora quello precedente di Pham e Stumpf.     

Unstable Process Identification in a Pure Thermal Plume under Forced Rotating Conditions

A pure thermal plume development arising from a finite-size rotating heat source was analyzed experimentally. Qualitative investigation through extensive visualization has brought into focus the existence of a threshold rotation frequency (i.e., a swirl number) above which stretching effects are strengthened, thereby forcing the ascending plume motion to spiral around the geometrical axis heat source. Nevertheless, above the threshold frequency (i.e., above the swirl number), unstable processes appear through flow field pulsation in close proximity to the heat source; the pulsations literally beat and drive the flow field vicinity. From a strictly quantitative point of view, the data underscore the fact that heat source rotation presents two opposed trends. Below the threshold frequency, the higher the frequency, the more the temperature level is concentrated on the plume axis. In contrast, at the strongest rotation frequencies studied, the opposite is observed. Above the threshold rotating frequency, the characteristic rotating time scale appears to be too short to interact with the characteristic plume time scale. As a consequence, rotation of the heat source enhances transition from laminar to turbulence.     

Enhanced Directed Evolution in Mammalian Cells Yields a Hyperefficient Pyrrolysyl tRNA for Noncanonical Amino Acid Mutagenesis

Heterologous tRNAs used for noncanonical amino acid (ncAA) mutagenesis in mammalian cells typically show poor activity. We recently introduced a virus-assisted directed evolution strategy (VADER) that can enrich improved tRNA mutants from naïve libraries in mammalian cells. However, VADER was limited to processing only a few thousand mutants; the inability to screen a larger sequence space precluded the identification of highly active variants with distal synergistic mutations. Here, we report VADER2.0, which can process significantly larger mutant libraries. It also employs a novel library design, which maintains base-pairing between distant residues in the stem regions, allowing us to pack a higher density of functional mutants within a fixed sequence space. VADER2.0 enabled simultaneous engineering of the entire acceptor stem of M. mazei pyrrolysyl tRNA (tRNA^Pyl), leading to a remarkably improved variant, which facilitates more efficient incorporation of a wider range of ncAAs, and enables facile development of viral vectors and stable cell-lines for ncAA mutagenesis.     

Sulforaphane Regulates eNOS Activation and NO Production via Src-Mediated PI3K/Akt Signaling in Human Endothelial EA.hy926 Cells

Sulforaphane (SFN) is a naturally occurring isothiocyanate that is abundant in many cruciferous vegetables, such as broccoli and cauliflower, and it has been observed to exert numerous biological activities. In the present study, we investigate the effect of SFN on eNOS, a key regulatory enzyme of vascular homeostasis and underlying intracellular pathways, in human endothelial EA.hy926 cells. The results indicate that SFN treatment significantly increases NO production and eNOS phosphorylation in a time- and dose-dependent fashion and also augments Akt phosphorylation in a time- and dose-dependent manner. Meanwhile, pretreatment with LY294002 (a specific PI3K inhibitor) suppresses the phosphorylation of eNOS and NO production. Furthermore, SFN time- and dose-dependently induces the phosphorylation of Src kinase, a further upstream regulator of PI3K, while PP2 pretreatment (a specific Src inhibitor) eliminates the increase in phosphorylated Akt, eNOS and the production of NO derived from eNOS. Overall, the present study uncovers a novel effect of SFN to stimulate eNOS activity in EA.hy926 cells by regulating NO bioavailability. These findings provide clear evidence that SFN regulates eNOS activity and NO bioavailability, suggesting a promising therapeutic candidate to prevent endothelial dysfunction, atherosclerosis and other cardiovascular diseases.     

Reversible addition–fragmentation chain‐transfer graft polymerization of styrene: Solid phases for organic and peptide synthesis

The γ‐initiated reversible addition–fragmentation chain‐transfer (RAFT)‐agent‐mediated free‐radical graft polymerization of styrene onto a polypropylene solid phase has been performed with cumyl phenyldithioacetate (CPDA). The initial CPDA concentrations range between 1 × 10^?2 and 2 × 10^?3 mol L^?1 with dose rates of 0.18, 0.08, 0.07, 0.05, and 0.03 kGy h^?1. The RAFT graft polymerization is compared with the conventional free‐radical graft polymerization of styrene onto polypropylene. Both processes show two distinct regimes of grafting: (1) the grafting layer regime, in which the surface is not yet totally covered with polymer chains, and (2) a regime in which a second polymer layer is formed. Here, we hypothesize that the surface is totally covered with polymer chains and that new polymer chains are started by polystyrene radicals from already grafted chains. The grafting ratio of the RAFT‐agent‐mediated process is controlled via the initial CPDA concentration. The molecular weight of the polystyrene from the solution (PS_free) shows a linear behavior with conversion and has a low polydispersity index. Furthermore, the loading of the grafted solid phase shows a linear relationship with the molecular weight of PS_free for both regimes. Regime 2 has a higher loading capacity per molecular weight than regime 1. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4180–4192, 2002     

Core-shell particles: building blocks for advanced polymer materials

Polymer particles with submicrometer dimensions show promising applications in “bottom-to-top approach” to fabrication of materials with periodic structure, function, and composition. A novel approach to producing such materials is proposed, which employs core-shell particles with specific structures and compositions. We report on the synthesis of core-shell particles using interfacial polymerization and heterocoagulation techniques. The compositions of core-forming material and/or the shell-forming polymers were selectively controlled to be make the cores or the shells rigid or fluid, fluorescent or non-fluorescent, organic or inorganic. Several potential applications of nanocomposite materials obtained from these particles are demonstrated, including three-dimensional optical data storage and optical limiting and switching.