Stealth Luminescent Organic Nanoparticles Made from Quadrupolar Dyes for Two-Photon Bioimaging: Effect of End-Groups and Core

Molecular-based Fluorescent Organic Nanoparticles (FONs) are versatile light-emitting nano-tools whose properties can be rationally addressed by bottom-up molecular engineering. A challenging property to gain control over is the interaction of the FONs’ surface with biological systems. Indeed, most types of nanoparticles tend to interact with biological membranes. To address this limitation, we recently reported on two-photon (2P) absorbing, red to near infrared (NIR) emitting quadrupolar extended dyes built from a benzothiadiazole core and diphenylamino endgroups that yield spontaneously stealth FONs. In this paper, we expand our understanding of the structure-property relationship between the dye structure and the FONs 2P absorption response, fluorescence and stealthiness by characterizing a dye-related series of FONs. We observe that increasing the strength of the donor end-groups or of the core acceptor in the quadrupolar (D-π-A-π-D) dye structure allows for the tuning of optical properties, notably red-shifting both the emission (from red to NIR) and 2P absorption spectra while inducing a decrease in their fluorescence quantum yield. Thanks to their strong 1P and 2P absorption, all FONs whose median size varies between 11 and 28 nm exhibit giant 1P (10⁶ M⁻¹.cm⁻¹) and 2P (10⁴ GM) brightness values. Interestingly, all FONs were found to be non-toxic, exhibit stealth behaviour, and show vanishing non-specific interactions with cell membranes. We postulate that the strong hydrophobic character and the rigidity of the FONs building blocks are crucial to controlling the stealth nano-bio interface.     

Synthesis of Carbon/Sulfur Nanolaminates by Electrochemical Extraction of Titanium from Ti2SC

Herein we electrochemically and selectively extract Ti from the MAX phase Ti₂SC to form carbon/sulfur (C/S) nanolaminates at room temperature. The products are composed of multi‐layers of C/S flakes, with predominantly amorphous and some graphene‐like structures. Covalent bonding between C and S is observed in the nanolaminates, which render the latter promising candidates as electrode materials for Li‐S batteries. We also show that it is possible to extract Ti from other MAX phases, such as Ti₃AlC₂ , Ti₃SnC₂ , and Ti₂GeC, suggesting that electrochemical etching can be a powerful method to selectively extract the “M” elements from the MAX phases, to produce “AX” layered structures, that cannot be made otherwise. The latter hold promise for a variety of applications, such as energy storage, catalysis, etc.     

Stability of ZSM-11 and BETA zeolites during the catalytic cracking of low-density polyethylene

The stability of H-ZSM-11 (H-Z) and H-BETA (H-B) zeolites during the catalytic degradation of low-density polyethylene (LDPE) was studied using the same sample of catalyst in eleven consecutive cycles. The gaseous hydrocarbons, liquid hydrocarbons and waxes generated in each cycle were analyzed as well as the used catalyst. The zeolites were characterized by XRD, FTIR of adsorbed pyridine and N₂ adsorption, while the physical mixtures of LDPE/zeolites were subjected to TG-DTG analysis.The H-Z zeolite exhibited an important stability during the successive cycles of LDPE conversion. On the contrary, the behavior H-B zeolite was completely different; from the sixth cycle the yields of products changed progressively, approaching to that obtained in a purely thermal process.The yields of accumulated coke increased steadily throughout the cycles up to maximum values in the eleventh cycle of ∼6 and ∼15 wt% for H-Z and H-B, respectively. These results were confirmed by TG under air flow.     

Nickel‐Catalyzed Carboxylation of Benzylic C−N Bonds with CO2

A user‐friendly Ni‐catalyzed reductive carboxylation of benzylic C?N bonds with CO₂ is described. This procedure outperforms state‐of‐the‐art techniques for the carboxylation of benzyl electrophiles by avoiding commonly observed parasitic pathways, such as homodimerization or β‐hydride elimination, thus leading to new knowledge in cross‐electrophile reactions.     

Borocyclopropanation of Styrenes Mediated by UV‐light Under Continuous Flow Conditions

Herein, we report a user‐friendly and metal‐free UV‐A light mediated borocyclopropanation of styrenes using continuous flow technology. A broad range of styrene derivatives can be cyclopropanated in good yields within 1 h residence time to produce highly valuable cyclopropylboronate esters with modest to good diastereoselectivities. The reaction is also applicable to α‐substituted styrenes. Mechanistic studies support a photoredox process during which xanthone, a well‐known organic photosensitizer, can easily reach a photoexcited state that is available for both an oxidative and a reductive quenching.     

Acidity modification by thermal and steam treatment in silica-alumina and its relation with methanol to hydrocarbons reaction

The physical properties as well as the acidity of an amorphous silica-alumina were modified by steam and thermal treatments and a general correlation (including samples modified by other methods) between hydrocarbon formation and surface acidity was obtained.

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