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651.
Nanoparticles agglomerate when in contact with biological solutions, depending on the solutions’ nature. The agglomeration state will directly influence cellular response, since free nanoparticles are prone to interact with cells and get absorbed into them. In sunscreens, titanium dioxide nanoparticles (TiO2-NPs) form mainly aggregates between 30 and 150 nm. Until now, no toxicological study with skin cells has reached this range of size distribution. Therefore, in order to reliably evaluate their safety, it is essential to prepare suspensions with reproducibility, irrespective of the biological solution used, representing the above particle size distribution range of NPs (30–150 nm) found on sunscreens. Thus, the aim of this study was to develop a unique protocol of TiO2 dispersion, combining these features after dilution in different skin cell culture media, for in vitro tests. This new protocol was based on physicochemical characteristics of TiO2, which led to the choice of the optimal pH condition for ultrasonication. The next step consisted of stabilization of protein capping with acidified bovine serum albumin, followed by an adjustment of pH to 7.0. At each step, the solutions were analyzed by dynamic light scattering and transmission electron microscopy. The final concentration of NPs was determined by inductively coupled plasma-optical emission spectroscopy. Finally, when diluted in dulbecco’s modified eagle medium, melanocytes growth medium, or keratinocytes growth medium, TiO2–NPs displayed a highly reproducible size distribution, within the desired size range and without significant differences among the media. Together, these results demonstrate the consistency achieved by this new methodology and its suitability for in vitro tests involving skin cell cultures.  相似文献   
652.
When the standard model is extended with right-handed neutrinos the symmetries of the resulting Lagrangian are enlarged with a new global U(1) R Abelian factor. In the context of minimal seesaw models we analyze the implications of a slightly broken U(1) R symmetry on charged lepton flavor violating decays. We find, depending on the R-charge assignments, models where charged lepton flavor violating rates can be within measurable ranges. In particular, we show that in the resulting models due to the structure of the light neutrino mass matrix muon flavor violating decays are entirely determined by neutrino data (up to a normalization factor) and can be sizable in a wide right-handed neutrino mass range.  相似文献   
653.
Velocity-encoded Cine magnetic resonance imaging (MRI) was used to measure blood flow in the anterior tibial artery (AT), posterior tibial artery (PT), and popliteal artery of adult human subjects (mean age 29 yr) before and after 90 s of ankle dorsiflexion exercise. Before exercise, mean flow, peak systolic velocity, and end-diastolic velocity in AT were 8.1 ± 1.6 (SE, n = 6) ml/min, 26.9 ± 2.6 cm/s, and −0.6 ± 0.4 cm/s, respectively. After exercise, mean flow and peak systolic velocity in AT increased by 19-fold and 3-fold, respectively, and end-diastolic velocity increased to 8.7 ± 1.1 cm/s. Flow in popliteal artery above its bifurcation was similar to the sum of flows in AT and PT, both before and after exercise. Flow in AT declined exponentially after exercise with a mean half-time of 4 min. The results demonstrate the utility of MR phase-encoded flow-velocity measurements for physiological studies of peripheral vascular dynamics after exercise.  相似文献   
654.
Because of compressibility criteria, fuel used in aeronautical combustors is liquid. Their numerical simulation therefore requires the modeling of two-phase flames, involving key phenomena such as injection, atomization, polydispersion, drag, evaporation and turbulent combustion. In the present work, particular modeling efforts have been made on spray injection and evaporation, and their coupling to turbulent combustion models in the Large Eddy Simulation (LES) approach. The model developed for fuel injection is validated against measurements in a non-evaporating spray in a quiescent atmosphere, while the evaporation model accuracy is discussed from results obtained in the case of evaporating isolated droplets. These models are finally used in reacting LES of a multipoint burner in take-off conditions, showing the complex two-phase flame structure.  相似文献   
655.
    
The modification of nickel with boron or phosphorus leads to significant enhancement of its electrocatalytic activity for the oxygen evolution reaction (OER). However, the precise role of the guest elements, B and P, in enhancing the OER of the host element (Ni) remains unclear. Herein, we present insight into the role of B and P in enhancing electrocatalysis of oxygen evolution by nickel borides and nickel phosphides. The apparent activation energy, Ea*, of electrocatalytic oxygen evolution on Ni2P was 78.4 kJ/mol, on Ni2B 65.4 kJ/mol, and on Ni nanoparticles 94.0 kJ/mol, thus revealing that both B and P affect the intrinsic activity of nickel. XPS data revealed shifts of −0.30 and 0.40 eV in the binding energy of the Ni 2p3/2 peak of Ni2B and Ni2P, respectively, with respect to that of pure Ni at 852.60 eV, thus indicating that B and P induce opposite electronic effects on the surface electronic structure of Ni. The origin of enhanced activity for oxygen evolution cannot, therefore, be attributed to such electronic modification or ligand effect. Severe changes induced on the nickel lattice, specifically, the Ni-Ni atomic order and interatomic distances (strain effect), by the presence of the guest atoms seem to be the dominant factors responsible for enhanced activity of oxygen evolution in nickel borides and nickel phosphides.  相似文献   
656.
    
The role of surface wetting properties and their impact on the performance of 3D printed microfluidic droplet generation devices for serial femtosecond crystallography (SFX) are reported. SFX is a novel crystallography method enabling structure determination of proteins at room temperature with atomic resolution using X‐ray free‐electron lasers (XFELs). In SFX, protein crystals in their mother liquor are delivered and intersected with a pulsed X‐ray beam using a liquid jet injector. Owing to the pulsed nature of the X‐ray beam, liquid jets tend to waste the vast majority of injected crystals, which this work aims to overcome with the delivery of aqueous protein crystal suspension droplets segmented by an oil phase. For this purpose, 3D printed droplet generators that can be easily customized for a variety of XFEL measurements have been developed. The surface properties, in particular the wetting properties of the resist materials compatible with the employed two‐photon printing technology, have so far not been characterized extensively, but are crucial for stable droplet generation. This work investigates experimentally the effectiveness and the long‐term stability of three different surface treatments on photoresist films and glass as models for our 3D printed droplet generator and the fused silica capillaries employed in the other fluidic components of an SFX experiment. Finally, the droplet generation performance of an assembly consisting of the 3D printed device and fused silica capillaries is examined. Stable and reproducible droplet generation was achieved with a fluorinated surface coating which also allowed for robust downstream droplet delivery. Experimental XFEL diffraction data of crystals formed from the large membrane protein complex photosystem I demonstrate the full compatibility of the new injection method with very fragile membrane protein crystals and show that successful droplet generation of crystal‐laden aqueous droplets intersected by an oil phase correlates with increased crystal hit rates.  相似文献   
657.
658.
    
A novel and useful method to catalyze the electro‐oxidation of nicotinamide adenine dinucleotide (NADH) over a glassy carbon electrode (GCE) modified with graphene oxide (GO) is presented. Based on the presence of oxygen moieties in GO, which can be easily reduced, an in situ electrochemical generation of reduced graphene oxide (denoted as erGO) applying a sufficient negative potential. A potential of ?1.000 V was selected to generate the erGO/GCE as a pretreatment potential before the detection of NADH. The in situ generated erGO/GCE system produces a decrease in the overpotential of NADH oxidation from +0.720 V to +0.230 V compared with GCE. The process also produced an important increase in current signals. The modified electrode was characterized by scanning electron (SEM) and electrochemical microscopies (SECM), cyclic voltammetry and by Raman spectroscopy. Amperometric detection of NADH via this straightforward electrocatalytic method provides a wide linear range between 10 and 100 μM, a lower detection limit of 0.36 μM and an excellent sensitivity of (1.47±0.09) μA mM?1.  相似文献   
659.
    
We report carbene insertion into Si?H bonds of polyhedral oligomeric silsesquioxanes (POSS) for the synthesis of highly functionalized siloxane nanomaterials. Dirhodium(II) carboxylates catalyze insertion of aryl-diazoacetates as carbene precursors to afford POSS structures containing both ester and aryl groups as orthogonal functional handles for further derivatization of POSS materials. Four diverse and structurally varied silsesquioxane core scaffolds with one, three, or eight Si?H bonds were evaluated with diazo reactants to produce a total of 20 new POSS compounds. Novel diazo compounds containing a fluorinated octyl group and boron-dipyrromethene (BODIPY) chromophore demonstrate the use of highly functionalized substrates. Transformations of aryl(ester)-functionalized POSS compounds derived from this method are demonstrated, including ester hydrolysis and Suzuki–Miyaura cross-coupling.  相似文献   
660.
    
Optimising catalyst materials for visible light-driven fuel production requires understanding complex and intertwined processes including light absorption and catalyst stability, as well as mass, charge, and energy transport. These phenomena can be uniquely combined (and ideally controlled) in porous host–guest systems. Towards this goal we designed model systems consisting of molecular complexes as catalysts and porphyrin metal–organic frameworks (MOFs) as light-harvesting and hosting porous matrices. Two MOF-rhenium molecule hybrids with identical building units but differing topologies (PCN-222 and PCN-224) were prepared including photosensitiser-catalyst dyad-like systems integrated via self-assembled molecular recognition. This allowed us to investigate the impact of MOF topology on solar fuel production, with PCN-222 assemblies yielding a 9-fold turnover number enhancement for solar CO2-to-CO reduction over PCN-224 hybrids as well as a 10-fold increase compared to the homogeneous catalyst-porphyrin dyad. Catalytic, spectroscopic and computational investigations identified larger pores and efficient exciton hopping as performance boosters, and further unveiled a MOF-specific, wavelength-dependent catalytic behaviour. Accordingly, CO2 reduction product selectivity is governed by selective activation of two independent, circumscribed or delocalised, energy/electron transfer channels from the porphyrin excited state to either formate-producing MOF nodes or the CO-producing molecular catalysts.

Two MOF molecular catalyst hybrids with differing topologies show mass and light transport governed photocatalysis. MOF-specific, irradiation wavelength-dependent product control is unlocked by switching between two energy/electron transfer channels.  相似文献   
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