A gadolinium-based magnetic ionic liquid for supramolecular dispersive liquid–liquid microextraction followed by HPLC/UV for the determination of favipiravir in human plasma

Favipiravir is a potential antiviral medication that has been recently licensed for Covid-19 treatment. In this work, a gadolinium-based magnetic ionic liquid was prepared and used as an extractant in dispersive liquid–liquid microextraction (DLLME) of favipiravir in human plasma. The high enriching ability of DLLME allowed the determination of favipiravir in real samples using HPLC/UV with sufficient sensitivity. The effects of several variables on extraction efficiency were investigated, including type of extractant, amount of extractant, type of disperser and disperser volume. The maximum enrichment was attained using 50 mg of the Gd-magnetic ionic liquid (MIL) and 150 μl of tetrahydrofuran. The Gd-based MIL could form a supramolecular assembly in the presence of tetrahydrofuran, which enhanced the extraction efficiency of favipiravir. The developed method was validated according to US Food and Drug Administration bioanalytical method validation guidelines. The coefficient of determination was 0.9999, for a linear concentration range of 25 to 1.0 × 10⁵ ng/ml. The percentage recovery (accuracy) varied from 99.83 to 104.2%, with RSD values (precision) ranging from 4.07 to 11.84%. The total extraction time was about 12 min and the HPLC analysis time was 5 min. The method was simple, selective and sensitive for the determination of favipiravir in real human plasma.     

Polymer 4D printing: Advanced shape-change and beyond

4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement.     

Advances in rapid and effective break-in/conditioning/recovery of automotive PEMFC stacks

Automotive proton exchange membrane fuel cell stacks need to meet manufacturer specified rated beginning-of-life (BOL) performance before being assembled into vehicles and shipped off to customers. The process of “breaking-in” of a freshly assembled stack is often referred to as “conditioning.” It has become an intensely researched area especially in automotive companies, where imminent commercialization of fuel cell electric vehicles (FCEVs) demands a short, energy- and cost-efficient, and practical conditioning protocol. Significant advances in reducing the conditioning time from 1 to 2 days to as low as 4h or less, in some cases without the use of additional inert gases such as nitrogen, and with minimal use of hydrogen, and specialized test stations will be discussed.     

On pointwise decay rates of time‐periodic solutions to the Navier–Stokes equation

We study the existence of a time‐periodic solution with pointwise decay properties to the Navier–Stokes equation in the whole space. We show that if the time‐periodic external force is sufficiently small in an appropriate sense, then there exists a time‐periodic solution $\{u,p\}$ of the Navier–Stokes equation such that $|{?}^j{u(t,x)|=O(|x|}^{1?n?j})$ and $|{?}^j{p(t,x)|=O(|x|}^{?n?j})(j=0,1,\dots )$ uniformly in $t\in \mathbb{R}$ as $|x|\to \infty$. Our solution decays faster than the time‐periodic Stokes fundamental solution and the faster decay of its spatial derivatives of higher order is also described.     

Application of microcrystalline cellulose as an efficient and cheap sorbent for the extraction of metoprolol from plasma and wastewater before HPLC–MS/MS determination

A dispersive solid-phase extraction method based on a new sorbent has been performed on plasma and wastewater samples to determine metoprolol by high-performance liquid chromatography–tandem mass spectrometry. In this study, the analyte was adsorbed from the samples onto microcrystalline cellulose as a green and efficient sorbent and then eluted for use in the determination step. In the mass spectrometer, the analyte was detected in the positive mode and selectivity of the analysis was increased by sequential mass analysis through multiple reaction monitoring. All of the effective parameters in the extraction of metoprolol from plasma and wastewater were optimized. Under optimal conditions the method was linear in the ranges of 1–1,000 and 0.1–1,000 ng/ml in plasma and wastewater samples, respectively. The detection limits of the method were 0.30 and 0.03 ng/ml in plasma and wastewater samples, respectively. The data showed that the method provides low detection limit, wide linear range, good precision and high extraction recovery. Finally several plasma and wastewater samples were successfully analyzed using the method. The use of a small amount of a green and inexpensive sorbent and a low volume of plasma without the need for further pretreatment steps are the main advantages of the method.     

Enhanced Power Density of Alcohol Biofuel Cell by Polymer-assisted Crosslinks of 3D Graphene on Carbon Paper as the Bioanode

Herein, we successfully construct the 3D biocompatible graphene through crosslinking 2D graphene nanosheet onto carbon fiber paper with poly(diallyldimethylammonium chloride) (PDDA) as anode of the alcohol biofuel cell. Compared with the bioanode without 3D graphene, the current density and output power of PDDA-graphene-ADH bioanode is increased by 23 % and 41 % at a high concentration of ethanol at pH 8.9, suggesting the stabilization role of graphene in enzyme loading. The study provides us a deep analysis on structures and performances of the bioanode incl. electrochemistry, X-ray photoelectron spectra, and atomic force microscopy images, which is significant to develop the new methods to construct 3D porous electrodes in energy conversion device.     

Edge-enriched graphene with boron and nitrogen co-doping for enhanced oxygen reduction reaction

Carbon-based electrocatalysts for oxygen reduction reaction (ORR), especially in anion exchange membrane fuel cells (AEMFCs), have received a lot of attention because they exhibit excellent stability and are comparable to commercial Pt/C catalysts. Currently, to maximize the catalytic activity of carbon-based electrocatalysts, there are two major strategies: heteroatom doping or exposing active edge sites. However, the approach of increasing heteroatomic dopants of active edge sites has been rarely addressed. In this study, we present a simple strategy to prepare edge-enriched graphene catalysts with an increased ratio of heteroatomic dopants suitable for ORR of AEMFCs. The catalysts were prepared under harsh oxidation conditions, followed by a simple co-doping process with boron and nitrogen. The ORR activity of the catalysts was observed to be related to an increase of edge sites with heteroatomic dopants. We believe that the edge-enriched structure leads to accelerated electron transfer with enhanced oxygen adsorption.     

Limitations of the Clausius‐Mossotti function used in dielectrophoresis and electrical impedance studies of biomacromolecules

Dielectrophoresis (DEP) studies have progressed from the microscopic scale of cells and bacteria, through the mesoscale of virions to the molecular scale of DNA and proteins. The Clausius‐Mossotti function, based on macroscopic electrostatics, is invariably employed in the analyses of all these studies. The limitations of this practice are explored, with the conclusion that it should be abandoned for the DEP study of proteins and modified for native DNA. For macromolecular samples in general, a DEP theory that incorporates molecular‐scale interactions and the influence of permanent dipoles is more appropriate. Experimental ways to test these conclusions are proposed.     

Fluid‐structure coupling of linear elastic model with compressible flow models

Cavitation erosion is caused in solids exposed to strong pressure waves developing in an adjacent fluid field. The knowledge of the transient distribution of stresses in the solid is important to understand the cause of damaging by comparisons with breaking points of the material. The modeling of this problem requires the coupling of the models for the fluid and the solid. For this purpose, we use a strategy based on the solution of coupled Riemann problems that has been originally developed for the coupling of 2 fluids. This concept is exemplified for the coupling of a linear elastic structure with an ideal gas. The coupling procedure relies on the solution of a nonlinear equation. Existence and uniqueness of the solution is proven. The coupling conditions are validated by means of quasi‐1D problems for which an explicit solution can be determined. For a more realistic scenario, a 2D application is considered where in a compressible single fluid, a hot gas bubble at low pressure collapses in a cold gas at high pressure near an adjacent structure.     

Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes

The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g^?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g^?1 for the CNOs/Ppy bilayer (electrochemical deposition).