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The electrochemical stability window of water is known to vary with the type and concentration of dissolved salts. However, the underlying influence of ions on the thermodynamic stability of aqueous solutions has not been fully understood. Here, we investigated the electrolytic behaviors of aqueous electrolytes as a function of different ions. Our findings indicate that ions with high ionic potentials, i.e., charge density, promote the formation of their respective hydration structures, enhancing electrolytic reactions via an inductive effect, particularly for small cations. Conversely, ions with lower ionic potentials increase the proportion of free water molecules—those not engaged in hydration shells or hydrogen-bonding networks—leading to greater electrolytic stability. Furthermore, we observe that the chemical environment created by bulky ions with lower ionic potentials impedes electrolytic reactions by frustrating the solvation of protons and hydroxide ions, the products of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. We found that the solvation of protons plays a more substantial role than that of hydroxide, which explains a greater shift for OER than for HER, a puzzle that cannot be rationalized by the notion of varying O−H bond strengths of water. These insights will help the design of aqueous systems.  相似文献   
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Secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) represent three surface analysis techniques heavily used in the complementary metal oxide semiconductor (CMOS) industry. The maturity of these techniques is demonstrated by (a) the diversity of lab-based instruments used in research and development (R&D) as well as to support fab-related issues and (b) the fact that highly automated platforms have now been or are being introduced into the fab for process control. Some recent developments of interest in the lab R&D space include the following: (a) the introduction of Orbitrap mass spectrometers into SIMS, (b) the introduction of higher energy monochromated photon sources into standalone lab-based XPS, and (c) the introduction of commercialized vacuum–scanning probe microscopy (SPM) platforms. The possibilities this opens are demonstrated through (a) SIMS analysis of organics from photoresist materials, (b) XPS subsurface analysis, ie, beyond the sputter front during depth profiling, and (c) SPM analysis of 2D material properties sensitive to the ambient environment, to mention a few.  相似文献   
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We consider the Cauchy problem for the equations of selfgravitating motions of a barotropic gas with density-dependent viscosities μ(ρ), and λ(ρ) satisfying the Bresch–Desjardins condition, when the pressure P(ρ) is not necessarily a monotone function of the density. We prove that this problem admits a global weak solution provided that the adiabatic exponent γ associated with P(ρ) satisfies ${\gamma > \frac{4}{3}}$ .  相似文献   
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Development of a volatile amine sensor for the monitoring of fish spoilage   总被引:8,自引:0,他引:8  
A sensor with potential for the development of a “chemical barcode” for real-time monitoring of fish freshness is described. This on-package sensor contains a pH sensitive dye, bromocresol green, that responds through visible colour change to basic volatile spoilage compounds, such as trimethylamine (TMA), ammonia (NH3) and dimethylamine (DMA) collectively known as Total Volatile Basic Nitrogen (TVB-N). The sensor characteristics were studied as well as its response with standard ammonia gas. Trials on cod and under-utilised species have verified that the sensor response correlates with bacterial growth patterns in fish samples thus enabling the “real-time” monitoring of spoilage in various fish species. The sensor response can be interrogated with a simple, inexpensive reflectance colorimeter that we have developed based on two light emitting diodes (LEDs) and a photodetector.  相似文献   
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The effect of a layer of electrochemically grafted 4‐diazo‐N,N‐diethylaniline (DEA) groups on the electron transfer kinetics of redox systems, displaying fast and slow heterogeneous electron transfer rate constants at edge and basal planes of carbon, was investigated. The properties of the modified electrode were characterized by cyclic voltammetry using four different inorganic redox systems (Fe(CN) , Co(phen) , Ru(NH3) , and IrCl in acidic, neutral, and basic media. Two distinct blocking behaviors and electrostatic effects were observed. More precisely, a strong blocking effect of the grafted layer on Fe(CN) and Co(phen) was found, whereas Ru(NH3) and IrCl showed to be rather unaffected by the presence of the DEA grafted layer.  相似文献   
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A stability-indicating reversed-phase high-performance liquid chromatographic method was developed and validated as per the International Conference on Harmonization (ICH) guidelines to evaluate the reproducibility of batches of synthetic peptides included in a stability program, in particular cholecystokinin (CCK-4) peptide.Both isothermal and nonisothermal approaches were used to determine stability under experimental conditions and the resulting degradation products were identified by liquid chromatography-mass spectrometry (LC-MS). The principal degradation product was the cyclic dimer, although another two products derived from it were also detected, due to the loss of one or two Phe-NH2 residues. The dimerization follows first-order kinetics, whereas the hydrolytic cleavage implies both consecutive and in-parallel processes. The linear Arrhenius plot indicates that the degradation mechanism and kinetics do not change with temperature or the batch, but the degradation rate does depend on the batch, for example, the shelf-life at 25 °C was 2.54 days for batch 3, which is 13-times lower than batch 2. This variability is caused by a change in the synthesis process introduced by the manufacturer.The combination of these two elements: the analytical and stability-evaluating methods provide enough data to establish a stability-indicating profile, as required by the guideline ICH-Q6B for biotechnological/biological products.  相似文献   
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