Preparation and characterization of octadecyl acrylate monoliths for capillary electrochromatography by photochemical,thermal, and chemical initiation†

Monolithic stationary phases based on octadecyl acrylate for CEC using different initiating systems (UV irradiation, thermal, and chemical initiation) in the presence of lauroyl peroxide as initiator were synthesized. For each initiation mode, the influence of the porogenic solvent composition on both the morphological and electrochromatographic properties of the resulting monoliths was investigated. Under optimal conditions, excellent efficiencies for the photochemically and chemically polymerized monoliths (minimum plate heights of 6.9–10.7 and 6.5–12.6 μm, respectively) were achieved. Thermally initiated columns gave lower efficiency values, permeabilities, and longer analysis times compared to these initiating systems. The produced monolithic stationary phases were evaluated in terms of reproducibility and gave RSD values below 9.2, 10.6, and 9.8% for UV, thermally, and chemically initiated columns, respectively.     

Galvanostatically Deposited PtNi Thin-Films as Electrocatalysts for the Hydrogen Evolution Reaction

The synthesis of hybrid platinum materials is fundamental to enable alkaline water electrolysis for cost-effective H₂ generation. In this work, we have used a galvanostatic method to co-deposit PtNi films onto polycrystalline gold. The surface concentrations of Ni (Γ_Ni) and Pt (Γ_Pt) were calculated from electrochemical measurements; the Γ_Pt/Γ_Ni ratio and electrocatalytic activity of these materials towards hydrogen evolution reaction (HER) in 1 M KOH show a strong dependence on the current density pulse applied during the electrodeposition. Analysis of the Tafel parameters hints that, on these deposits, HER proceeds through a Volmer-Heyrovsky mechanism. The galvanostatically deposited PtNi layers present a high current output per Pt gram, 3199 A g_Pt⁻¹, which is significantly larger compared to other PtNi-based materials obtained by more extended and more complex synthesis methods.     

Electro-flow focusing: the high-conductivity low-viscosity limit

Electro-flow focusing, a technique combining the features of electrospray (ES) and flow focusing (FF), provides a reliable tool to reach parametrical microjetting ranges not attainable by ES or FF alone under specific operational regimes (liquid properties and flow rate). In this Letter, we provide not only a closed theoretical model predicting the diameter of a high electrical conductivity electro-flow focused liquid microjet, but also its convective or absolute instability, linked to the jetting-to-dripping transition and the minimum liquid flow rate that can be ejected in steady jetting regime, in which the smallest droplets are issued. Good agreement is found with experimental values.     

Real‐Time In Vivo Detection of Cellular Senescence through the Controlled Release of the NIR Fluorescent Dye Nile Blue

In vivo detection of cellular senescence is accomplished by using mesoporous silica nanoparticles loaded with the NIR‐FDA approved Nile blue (NB) dye and capped with a galactohexasaccharide ( S3 ). NB emission at 672 nm is highly quenched inside S3 , yet a remarkable emission enhancement is observed upon cap hydrolysis in the presence of β‐galactosidase and dye release. The efficacy of the probe to detect cellular senescence is tested in vitro in melanoma SK‐Mel‐103 and breast cancer 4T1 cells and in vivo in palbociclib‐treated BALB/cByJ mice bearing breast cancer tumor.     

Duality Functors for Triple Vector Bundles

We calculate the group of dualization operations for triple vector bundles, showing that it has order 96 and not 72 as given in Mackenzie’s original treatment. The group is a nonsplit extension of S ₄ by the Klein group. Dualization operations are interpreted as functors on appropriate categories and are said to be equal if they are naturally isomorphic. The method set out here will be applied in a subsequent paper to the case of n-fold vector bundles.     

A review of robust clustering methods

Deviations from theoretical assumptions together with the presence of certain amount of outlying observations are common in many practical statistical applications. This is also the case when applying Cluster Analysis methods, where those troubles could lead to unsatisfactory clustering results. Robust Clustering methods are aimed at avoiding these unsatisfactory results. Moreover, there exist certain connections between robust procedures and Cluster Analysis that make Robust Clustering an appealing unifying framework. A review of different robust clustering approaches in the literature is presented. Special attention is paid to methods based on trimming which try to discard most outlying data when carrying out the clustering process.     

A semi-empirical approach to determine gamma activities in environmental cylindrical samples

A semi-empirical method to determine radionuclide concentrations in large environmental samples without the use of reference material and avoiding the typical complexity of Monte-Carlo codes is proposed. The calculation of full-energy peak efficiencies was carried out from a relative efficiency curve (obtained from the gamma spectra data), and the geometric (simulated by Monte-Carlo), absorption, sample and intrinsic efficiencies for energies between 130 and 3000 keV. The absorption and sample efficiencies were determined from the mass absorption coefficients, whereas the intrinsic efficiency was approximated by an empirical function. The deviations between calculated and experimental efficiencies for a reference material in most cases are less than 10%. Radionuclide activities in marine sediment samples calculated by the proposed method and by the experimental comparative method were not significantly different. This new method can be used for routine environmental monitoring when uncertainties up to 10% are acceptable.