Nanometer-sized materials for solid-phase extraction of trace elements

This review presents a comprehensive update on the state-of-the-art of nanometer-sized materials in solid-phase extraction (SPE) of trace elements followed by atomic-spectrometry detection. Zero-dimensional nanomaterials (fullerene), one-dimensional nanomaterials (carbon nanotubes, inorganic nanotubes, and nanowires), two-dimensional nanomaterials (nanofibers), and three-dimensional nanomaterials (nanoparticles, mesoporous nanoparticles, magnetic nanoparticles, and dendrimers) for SPE are discussed, with their application for trace-element analysis and their speciation in different matrices. A variety of other novel SPE sorbents, including restricted-access sorbents, ion-imprinted polymers, and metal–organic frameworks, are also discussed, although their applications in trace-element analysis are relatively scarce so far.

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Graphical Abstract Nanometer-sized materials for solid-phaseextraction of trace elements and their species

     

High-internal-phase-emulsion polymeric monolith coupled with liquid chromatography–electrospray tandem mass spectrometry for enrichment and sensitive detection of trace cytokinins in plant samples

High-internal-phase-emulsion polymers (polyHIPEs) show great promise as solid-phase-extraction (SPE) materials because of the tremendous porosity and highly interconnected framework afforded by the high-internal-phase-emulsion (HIPE) technique. In this work, polyHIPE monolithic columns as novel SPE materials were prepared and applied to trace enrichment of cytokinins (CKs) from complex plant samples. The polyHIPE monoliths were synthesized via the in-situ polymerization of the continuous phase of a HIPE containing styrene (STY) and divinylbenzene (DVB) in a stainless column, and revealed highly efficient and selective enrichment ability for aromatic compounds. Under the optimized experimental conditions, a method using a monolithic polyHIPE column combined with liquid chromatography–electrospray tandem mass spectrometry (LC–MS–MS) was developed for the simultaneous extraction and sensitive determination of trans-zeatin (tZ), meta-topolin (mT), kinetin (K), and kinetin riboside (KR). The proposed method had good linearity, with correlation coefficients (R ²) from 0.9957 to 0.9984, and low detection limits (LODs, S/N?=?3) in the range 2.4–47 pg mL^?1 for the four CKs. The method was successfully applied to the determination of CKs in real plant samples, and obtained good recoveries ranging from 68.8 % to 103.0 % and relative standard deviations (RSDs) lower than 16 %.     

A cationic cysteine-hydrazide as an enrichment tool for the mass spectrometric characterization of bacterial free oligosaccharides

In Campylobacterales and related ε-proteobacteria with N-linked glycosylation (NLG) pathways, free oligosaccharides (fOS) are released into the periplasmic space from lipid-linked precursors by the bacterial oligosaccharyltransferase (PglB). This hydrolysis results in the same molecular structure as the oligosaccharide that is transferred to a protein to be glycosylated. This allowed for the general elucidation of the fOS-branched structures and monosaccharides from a number of species using standard enrichment and mass spectrometry methods. To aid characterization of fOS, hydrazide chemistry has often been used for chemical modification of the reducing part of oligosaccharides resulting in better selectivity and sensitivity in mass spectrometry; however, the removal of the unreacted reagents used for the modification often causes the loss of the sample. Here, we develop a more robust method for fOS purification and characterize glycostructures using complementary tandem mass spectrometry (MS/MS) analysis. A cationic cysteine hydrazide derivative was synthesized to selectively isolate fOS from periplasmic fractions of bacteria. The cysteine hydrazide nicotinamide (Cyhn) probe possesses both thiol and cationic moieties. The former enables reversible conjugation to a thiol-activated solid support, while the latter improves the ionization signal during MS analysis. This enrichment was validated on the well-studied Campylobacter jejuni by identifying fOS from the periplasmic extracts. Using complementary MS/MS analysis, we approximated data of a known structure of the fOS from Campylobacter concisus. This versatile enrichment technique allows for the exploration of a diversity of protein glycosylation pathways.     

Loop formation and stability of self-avoiding polymer chains

Using 3-dimensional Langevin dynamics simulations, we investigated the dynamics of loop formation of chains with excluded volume interactions, and the stability of the formed loop. The mean looping time τ _l scales with chain length N and corresponding scaling exponent α increases linearly with the capture radius scaled by the Kuhn length a/l due to the effect of finite chain length. We also showed that the probability density function of the looping time is well fitted by a single exponential. Finally, we found that the mean unlooping time τ _u hardly depends on chain length N for a given a/l and that the stability of a formed loop is enhanced with increasing a/l.     

Selective adsorption of metronidazole on conjugated microporous polymers

Conjugated microporous polymers (CMPs) have recently received extensive attention in oil/organic solvent-water separation field as a kind of ideal porous absorbents with tunable porosity, large surface areas, and super-hydrophobicity. However, reports on the application of CMPs in adsorption of hydrophilic contaminants from water are very few. In this work, we studied the adsorption of metronidazole (MNZ), a polar antibiotic, by two kinds of CMPs. The adsorption characteristics of MNZ by the CMPs, including adsorption kinetics, mechanism, and isotherm parameters were calculated. The adsorption kinetics of MNZ was well expressed by the pseudo-second-order model, and the adsorption process was found to be mainly controlled by film diffusion. The adsorption isotherm data agreed well with the Langmuir isotherm model, and the values of free energy E indicated that the adsorption nature of MNZ on the CMPs was physisorption. Increasing dispersion degree of the CMPs in MNZ solution resulted in greater adsorption. This work may provide fundamental guidance for the removal of antibiotics by CMPs.     

On the manipulability of competitive equilibrium rules in many-to-many buyer–seller markets

We analyze the manipulability of competitive equilibrium allocation rules for the simplest many-to-many extension of Shapley and Shubik’s (Int J Game Theory 1:111–130, 1972) assignment game. First, we show that if an agent has a quota of one, then she does not have an incentive to manipulate any competitive equilibrium rule that gives her her most preferred competitive equilibrium payoff when she reports truthfully. In particular, this result extends to the one-to-many (respectively, many-to-one) models the Non-Manipulability Theorem of the buyers (respectively, sellers), proven by Demange (Strategyproofness in the assignment market game. École Polytechnique, Laboratoire d’Économetrie, Paris, 1982), Leonard (J Polit Econ 91:461–479, 1983), and Demange and Gale (Econometrica 55:873–888, 1985) for the assignment game. Second, we prove a “General Manipulability Theorem” that implies and generalizes two “folk theorems” for the assignment game, the Manipulability Theorem and the General Impossibility Theorem, never proven before. For the one-to-one case, this result provides a sort of converse of the Non-Manipulability Theorem.     

Flow auctions

Flow goods (like electricity) are sold through auctions in a dynamic framework. An important design question is the frequency of such auctions. We use a simple dynamic auction model in continuous time to answer this question. We focus on the relationship between the persistency of bidders’ valuations and the optimal choice of frequency. If the seller focuses on the equilibrium in which bidders follow a repeated static Nash strategy, then the frequency of auctions should typically increase when persistency declines. However, accounting for the fact that bidders can follow different equilibria that are collusive in nature, the comparative statics are reversed, forcing the seller to reduce the frequency when bidders’ valuations are less persistent. The argument builds on the fact that high frequency auctions are more conducive to collusion among bidders.     

Mechanism design for land acquisition

We consider the issue of designing Bayesian incentive-compatible, efficient, individually rational and balanced mechanisms for Land Acquisition. This is a problem of great practical importance in developing countries. Several sellers, each with one unit of land, are located at the nodes of a graph. Two sellers are contiguous if they are connected by an edge in the graph. The buyer realizes a positive value only if he can purchase plots that constitute a path of given length. Our main result is that there is a robust set of priors for which successful mechanisms exist when there are at least two distinct feasible sets of contiguous sellers. The analysis also identifies the role of critical sellers who lie on all such feasible sets.     

Optimal signaling with cheap talk and money burning

We study Sender-optimal signaling equilibria with cheap talk and money-burning. Under general assumptions, the Sender never uses money-burning to reveal all states, but always wants to garble information for at least some states. With quadratic preferences and any log-concave density of the states, optimal communication is garbled for all states: money-burning, if used at all, is used to adjust pooling intervals. This is illustrated by studying in depth the well-known uniform-quadratic case. We also show how the presence of a cost of being “caught unprepared” that gives rise to a small change in a common assumption on the Receiver’s utility function makes full revelation through money-burning Sender-optimal.     

Correlation and unmediated cheap talk in repeated games with imperfect monitoring

This paper studies n-player \((n\ge 3)\) undiscounted repeated games with imperfect monitoring. We prove that all uniform communication equilibrium payoffs of a repeated game can be obtained as Nash equilibrium payoffs of the game extended by unmediated cheap talk. We also show that all uniform communication equilibrium payoffs of a repeated game can be reached as Nash equilibrium payoffs of the game extended by a pre-play correlation device and a cheap-talk procedure that only involves public messages; furthermore, in the case of imperfect public and deterministic signals, no cheap talk is conducted on the equilibrium path.