Aryl‐Phosphonate Lanthanide Complexes and Their Fluorinated Derivatives: Investigation of Their Unusual Relaxometric Behavior and Potential Application as Dual Frequency 1H/19F MRI Probes

A series of low molecular weight lanthanide complexes were developed that have high ¹H longitudinal relaxivities (r₁) and the potential to be used as dual frequency ¹H and ¹⁹F MR probes. Their behavior was investigated in more detail through relaxometry, pH‐potentiometry, luminescence, and multinuclear NMR spectroscopy. Fitting of the ¹H NMRD and ¹⁷O NMR profiles demonstrated a very short water residence lifetime (<10 ns) and an appreciable second sphere effect. At lower field strengths (20 MHz), two of the complexes displayed a peak in r₁ (21.7 and 16.3 mM ^?1 s^?1) caused by an agglomeration, that can be disrupted through the addition of phosphate anions. NMR spectroscopy revealed that at least two species are present in solution interconverting through an intramolecular binding process. Two complexes provided a suitable signal in ¹⁹F NMR spectroscopy and through the selection of optimized imaging parameters, phantom images were obtained in a MRI scanner at concentrations as low as 1 mM . The developed probes could be visualized through both ¹H and ¹⁹F MRI, showing their capability to function as dual frequency MRI contrast agents.     

Surfactant Hydrogels for the Dispersion of Carbon‐Nanotube‐Based Catalysts

Novel hydrogel phases based on positively charged and zwitterionic surfactants, namely, N‐[p‐(n‐dodecyloxybenzyl)]‐N,N,N‐trimethylammonium bromide (pDOTABr) and p‐dodecyloxybenzyldimethylamine oxide (pDOAO), which combine pristine carbon nanotubes (CNTs), were obtained, thus leading to stable dispersions and enhanced cross‐linked networks. The composite hydrogel featuring a well‐defined nanostructured morphology and an overall positively charged surface was shown to efficiently immobilise a polyanionic and redox‐active tetraruthenium‐substituted polyoxometalate (Ru₄POM) by complementary charge interactions. The resulting hybrid gel has been characterised by electron microscopy techniques, whereas the electrostatic‐directed assembly has been monitored by means of fluorescence spectroscopy and ζ‐potential tests. This protocol offers a straightforward supramolecular strategy for the design of novel aqueous‐based electrocatalytic soft materials, thereby improving the processability of CNTs while tuning their interfacial decoration with multiple catalytic domains. Electrochemical evidence confirms that the activity of the catalyst is preserved within the gel media.     

Electrochemical derivatization‐capillary electrophoresis‐contactless conductivity detection: A versatile strategy for simultaneous determination of cationic,anionic, and neutral analytes

The simultaneous determination of cationic, anionic, and neutral analytes in a real sample was demonstrated by coupling electrochemical (EC) derivatization with counter‐EOF CE‐C⁴D. An EC flow cell was used to oxidize alcohols from an antiseptic mouthwash sample into carboxylic acids at a platinum electrode in acid medium. The carboxylates formed in the derivatization process and other sample ingredients, such as benzoate, saccharinate, and sodium ions, were separated in counter‐flow mode and detected in one run in Tris‐HCl buffer, pH 8.6. Fewer than 5 min were needed to complete each analysis with the automated flow system comprising solenoid pumps for the management of solutions. Insights into the electrochemistry of benzoic acid, present in the sample matrix, were also gained by EC‐CE‐C⁴D; more specifically, by applying potentials higher than 1.47 V to the platinum electrode, some formiate and minute amounts of salicylate were detected.     

Microextraction by packed sorbent liquid chromatography with time‐of‐flight mass spectrometry of triazines employing a molecularly imprinted polymer†

Molecularly imprinted polymers for the determination of triazines were synthesized by precipitation using atrazine as template, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslinker, and 2,2′‐azobisisobutrynitrile as initiator. The polymers were characterized by infrared spectroscopy and scanning electron microscopy and packed in a device for microextraction by packed sorbent aiming for the preconcentration/cleanup of herbicides, such as atrazine, simazine, simetryn, ametryn, and terbutryn in corn samples. Liquid chromatography coupled with time‐of‐flight mass spectrometry was used for the separation and determination of the herbicides. The selectivity coefficient of molecularly imprinted polymers was compared with that of nonimprinted polymer for the binary mixtures of atrazine/propanil and atrazine/picloram, and the values obtained were 15.6 and 2.96, respectively. The analytical curve ranged from 10 to 80 μg/kg (r = 0.989) and the limits of detection and quantification in the corn matrices were 3.3 and 10 μg/kg, respectively. Intra‐ and interday precisions were < 14.8% and accuracy was better than 90.9% for all herbicides. Polymer synthesis was successfully applied to the cleanup and preconcentration of triazines from fortified corn samples with 91.1–109.1% of recovery.     

Polyaspartamide–Polylactide Graft Copolymers with Tunable Properties for the Realization of Fluorescent Nanoparticles for Imaging

Here, the synthesis and the characterization of novel amphiphilic graft copolymers with tunable properties, useful in obtaining polymeric fluorescent nanoparticles for application in imaging, are described. These copolymers are obtained by chemical conjugation of rhodamine B (RhB) moieties, polylactic acid (PLA), and O‐(2‐aminoethyl)‐O′‐methyl poly(ethylene glycol) (PEG) on α,β‐poly(N‐2‐hydroxyethyl)‐d,l ‐aspartamide (PHEA). In particular, PHEA is first functionalized with RhB to obtain PHEA–RhB with a derivatization degree in RhB (DD_RhB) equal to 0.55 mol%. By varying the reaction conditions, different amounts of PLA are grafted on PHEA–RhB to obtain PHEA‐RhB‐PLA with DD_PLA equal to 1.9, 4.0, and 6.2 mol%. Then, PEG chains are grafted on PHEA‐RhB‐PLA derivatives to obtain PHEA‐RhB‐PLA‐PEG graft copolymers. The preparation of polymeric fluorescent nanoparticles with tunable properties and spherical shape is described by using PHEA‐RhB‐PLA‐PEG with DD in PLA and PEG equal to 4.0 and 4.9 mol%, by following easily scaling up processes, such as emulsion‐solvent evaporation and high pressure homogenization (HPH)‐solvent evaporation techniques.

     

Determination of parabens in wastewater samples via robot-assisted dynamic single-drop microextraction and liquid chromatography–tandem mass spectrometry

Dynamic single-drop microextraction (SDME) was automatized employing an Arduino-based lab-made Cartesian robot and implemented to determine parabens in wastewater samples in combination with liquid chromatography–tandem mass spectrometry. A dedicated Arduino sketch controls the auto-performance of all the stages of the SDME process, including syringe filling, drop exposition, solvent recycling, and extract collection. Univariate and multivariate experiments investigated the main variables affecting the SDME performance, including robot-dependent and additional operational parameters. Under selected conditions, limit of detections were established at 0.3 µg/L for all the analytes, and the method provided linear responses in the range between 0.6 and 10 µg/L, with adequate reproducibility, measured as intraday relative standard deviations (RSDs) between 5.54% and 17.94%, (n = 6), and inter-days RSDs between 8.97% and 16.49% (n = 9). The robot-assisted technique eased the control of dynamic SDME, making the process more feasible, robust, and reliable so that the developed setup demonstrated to be a competitive strategy for the automated extraction of organic pollutants from water samples.     

Photoactivatable V-Shaped Bifunctional Quinone Methide Precursors as a New Class of Selective G-quadruplex Alkylating Agents

Combining the selectivity of G-quadruplex (G4) ligands with the spatial and temporal control of photochemistry is an emerging strategy to elucidate the biological relevance of these structures. In this work, we developed six novel V-shaped G4 ligands that can, upon irradiation, form stable covalent adducts with G4 structures via the reactive intermediate, quinone methide (QM). We thoroughly investigated the photochemical properties of the ligands and their ability to generate QMs. Subsequently, we analyzed their specificity for various topologies of G4 and discovered a preferential binding towards the human telomeric sequence. Finally, we tested the ligand ability to act as photochemical alkylating agents, identifying the covalent adducts with G4 structures. This work introduces a novel molecular tool in the chemical biology toolkit for G4s.