Fluorogenic hyaluronan nanogels for detection of micro- and nanoplastics in water

Environmental pollution from plastics is exponentially increasing due to human activities. While larger microplastics can be detected with various methods, retrieving micron-sized fragments and nanoplastics remains challenging. Yet, these smaller-sized plastics have been raising considerable toxicological concern. Here, we show that a poorly emissive hyaluronan functionalized with rhodamine B (HA–RB) adheres with high affinity to various microplastic surfaces, becoming brightly emissive. Micro- and nanoplastics (MNPs) can be successfully detected with size as small as the diffraction limit of confocal microscopy (ca. 250 nm). FLIM images show that the fluorescence lifetime of the dye moieties changes according to the plastics, making possible a discrimination of the nature of MNPs based on lifetime. HA–RB, compared to previous reports, eliminates false-positive results caused by formation of dye aggregates, resulting in a higher S/N ratio which allows the unequivocal detection of nano-sized fragments

PluS Nanoparticles Loaded with Sorafenib: Synthetic Approach and Their Effects on Endothelial Cells

Silica nanostructures are widely investigated for theranostic applications, since relatively mild and easy synthetic methods allow the fabrication of multi-compartment nanoparticles (NPs) and to finely modulate their properties. Here, we report the optimization of a synthetic strategy leading to brightly fluorescent silica NPs with a high loading ability – up to 45 molecules per NP – of Sorafenib, a small molecule acting as antiangiogenic drug. We demonstrate that these NPs can efficiently release the drug and they are able to inhibit endothelial cell proliferation, migration and network formation. Their lyophilization can endow them with long shelf stability while, once in solution, they show a much slower release compared to analogous micellar systems. Interestingly, Sorafenib released from PluS NPs completely prevented endothelial cell responses and post-receptor MAPK signaling ignited by VEGF, one of the major player of tumor angiogenesis. Our results indicate that these theranostic systems represent a promising structure for anti-cancer applications since NPs alone have no cytotoxic effect on cultured endothelial cells, a cell type to which drugs and exogenous material are always in contact once delivere

Photoluminescence-Based Techniques for the Detection of Micro- and Nanoplastics

The growing numbers related to plastic pollution are impressive, with ca. 70 % of produced plastic (>350 tonnes/year) being indiscriminately wasted in the environment. The most dangerous forms of plastic pollution for biota and human health are micro- and nano-plastics (MNPs), which are ubiquitous and more bioavailable. Their elimination is extremely difficult, but the first challenge is their detection since existing protocols are unsatisfactory for microplastics and mostly absent for nanoplastics. After a discussion of the state of the art for MNPs detection, we specifically revise the techniques based on photoluminescence that represent very promising solutions for this problem. In this context, Nile Red staining is the most used strategy and we show here its pros and limitations, but we also discuss other more recent approaches, such as the use of fluorogenic probes based on perylene-bisimide and on fluorogenic hyaluronan nanogels, with the added values of biocompatibility and water solubility

Towards a More Sustainable Photocatalyzed α-Arylation of Amines: Green Solvents, Catalyst Recycling and Low Loading

A more sustainable and efficient protocol for the photocatalytic α-amino arylation promoted by fac-Ir(ppy)3 was developed. Three noteworthy results were achieved: i) the replacement of toxic medium DMA with the greener solvents NBP and NHP, and the concurrent improvement of the process efficiency by lowering both the amine and the base amount; ii) the development of a recycling protocol for both the sustainable solvent NHP and the commercially available costly photocatalyst fac-Ir(ppy)3, achieving environmental and economic benefits. This approach to the photocatalyst recovery avoids very demanding catalyst structural modifications; iii) the protocol in green solvents proved to be scalable up to 10 mmol of limiting reagent, maintaining excellent performance also lowering the photocatalyst loading down to 0.05 mol%. This is the first example of photocatalytic α-arylation of amines promoted by such a low amount of catalyst. Lastly, the versatility of this approach was demonstrated by extending the use of the green solvent NBP to another photoredox process

Chemodivergent Photocatalytic Synthesis of Dihydrofurans and β,γ-Unsaturated Ketones

A synthetic procedure, catalysed by Ir(ppy)3 under visible-light irradiation, for the chemodivergent synthesis of 2,3-dihydrofurans (3) or β,γ-unsaturated ketones (7) starting from α-halo ketones (1) and alkenes (2) has been developed. The mild reaction conditions and the redox-neutral nature of the process make it particularly sustainable avoiding the use of both sacrificial reactants and stoichiometric strong oxidants. Careful experimental investigations, supported by DFT calculations, allowed to disclose in details a possible mechanistic pathway and to direct the synthesis chemodivergently either toward 3 or 7, depending not only on the nature of the substrates, but also on the choice of the experimental conditions. (Figure presented.)

Allenamides Playing Domino: A Redox-Neutral Photocatalytic Synthesis of Functionalized 2-Aminofurans

A photoredox catalytic synthesis of functionalized 2-aminofurans is proposed starting from α-halo carbonyl substrates and N-allenamides. The protocol proves to be efficient and sustainable thanks to: i) the use of visible light as green energy source, ii) the redox-neutral nature of the transformation, allowing to avoid additives and strong oxidants, iii) the mild reaction conditions and the functional groups tolerance, iv) the low photocatalyst loading and the absence of excess reagents, v) the one-pot formation of three new bonds in a domino sequence. According to our mechanistic hypothesis, the transformation is configured as a double radical-polar crossover reaction, in which the photocatalyst is excited, oxidized and reduced twice for each molecule of 2-aminofuran produced. The novelty of the designed synthetic approach also lies in the use of N-allenamides as substrates, which, after the addition of the first electrophilic radical, preserve a further reactive π-system, making possible the addition of a second α-keto radical and enabling the installation of a keto functionality at a remote position. The good yields, the broad scope, and the possibility to further synthetically elaborate the obtained furans make this protocol particularly promising for the construction of useful products. (Figure presented.)

Tandem Dye-Doped Nanoparticles for NIR Imaging via Cerenkov Resonance Energy Transfer

The detection of the Cerenkov radiation (CR) is an emerging preclinical imaging technique which allows monitoring the in vivo distribution of radionuclides. Among its possible advantages, the most interesting is the simplicity and cost of the required instrumentation compared, e.g., to that required for PET scans. On the other hand, one of its main drawbacks is related to the fact that CR, presenting the most intense component in the UV-vis region, has a very low penetration in biological tissues. To address this issue, we present here multifluorophoric silica nanoparticles properly designed to efficiently absorb the CR radiation and to have a quite high fluorescence quantum yield (0.12) at 826 nm. Thanks to a highly efficient series of energy transfer processes, each nanoparticle can convert part of the CR into NIR light, increasing its detection even under 1.0-cm thickness of muscle

Blending or Bonding? Mechanochromism of an Aggregachromic Mechanophore in a Thermoplastic Elastomer

A straightforward way for the preparation of mechanochromic polymers consists of incorporating a suitable content of a mechanophore in the polymeric matrix either by physical dispersion or via covalent functionalization. Although covalent incorporation may require demanding chemical efforts, this approach can offer significant advantages over physical dispersion. In this work, a common thermoplastic elastomer, styrene-b-(ethylene-co-butylene)-b-styrene triblock copolymer grafted with maleic anhydride (SEBS-MAH), was covalently functionalized with 1-aminomethylpyrene (AMP). MAH functional groups are covalently linked to the ethylene-co-butylene blocks, thus allowing a precise and selective confinement of the chromogenic AMP units in the soft block. Flat, fully conjugated pyrene units undergo the reversible formation of π-πaggregates, readily distinguishable by their red-shifted emission. These aggregates were heavily affected by the application of mechanical stimuli. Despite the low degree of mechanophore functionalization (about 1 wt %), uniaxial deformation of the polymer was reliably monitored via fluorescence and a clear drop in the excimer to monomer emission ratio (IE/IM) was observed starting from 50% of strain. The marked mechanochromism was confirmed by emission lifetime measurements and also by near-field investigations. In addition, the mechanoresponse showed good reversibility after repeated stress-relaxation cycles. Control experiments performed on formulations comprising a physical dispersion of pyrene in unfunctionalized SEBS showed faint excimer emission and a negligible mechanochromic response up to 5 wt % of doping, in substantial agreement with the scanning near-field optical microscopy analysis. An evident drop of the IE/IM ratio occurred for 10 wt % of pyrene, albeit the excimer emission remained predominant even at the highest deformation, being a smaller fraction of pyrene moieties involved. Overall, the covalent approach appeared as an elegant procedure to confine the chromogenic unit in the soft phase of block copolymers and thus to provide an elastomeric film showing a detectable and reversible mechanochromic response with a modest (i.e., ∼1 wt %) amount of pyrene molecules, i.e., 10 times smaller compared to the dispersed system

New lanthanide metalloligands and their use for the assembly of Ln-Ag bimetallic coordination frameworks : stepwise modular synthesis, structural characterization, and optical properties

Stepwise self-assembly processes using new lanthanide metalloligands (Ln-MLs) and silver salts have been successfully applied to isolate 4f-4d heterometallic coordination networks of four different structural types. In particular, the new lanthanide tetrakis-chelate complexes NEt4[Ln(L1)4] [HL1 = 1,3-bis(4\u2032-cyanophenyl)-1,3-propanedione; Ln = Eu (1a), La (1b), Nd (1c), Tb (1d)] and NEt4[Ln(L2)4] (HL2 = 1,3-bis(4\u2032-pyridyl)-1,3-propanedione; Ln = Eu (1e), Nd (1f)] have been synthetized, characterized and reacted with different silver salts. The use of NEt4[Ln(L1)4] allowed then to isolate and characterize i) neutral one-dimensional ladder-like species of formula [Ln(L1)4Ag] [Ln = Eu (2a), La(2b), Nd(2c), Tb(2d)] and ii) their supramolecular isomers [Ln(L1)4Ag] [Ln = Eu (3a), La (3b), Nd (3c), Tb (3d)] showing a very unstable 2D network structure, iii) the cationic 2D species [Ln(L1)4Ag2]X [Ln = Eu, X = PF6\u203e, CF3SO3\u203e, ClO4\u203e (4a\u20134c); Ln = Tb, Nd, La X = PF6\u203e (4d\u20134f)] and, only for lanthanum, iv) a fourth 2D species of formula [La(L1)4(H2O)Ag] (5) and sql topology. Of the eight nitrile groups on the MLs potentially coordinating, only a partial number is used for networking with Ag(I), that is, only two in families 2 and 3, and four in family 4 and in network 5. Finally, the four structural types are rationalized in terms of a new \u201cpincer-like\u201d Secondary Building Unit (SBU) consisting of a silver cation coordinating two central carbon atoms (\uf067 carbon) of two different diketonate ligands on the same ML. Therefore, it is shown that compounds 5, 4 and 2\u20133 contain, respectively, none, one or two of such pincer-like SBUs. The luminescence properties of the Ln-MLs and some of their polymeric species have been also investigated in solution and in the solid state