A Far-Red Emitting Fluorescent Chemogenetic Reporter for In Vivo Molecular Imaging

Far-red emitting fluorescent labels are highly desirable for spectral multiplexing and deep tissue imaging. Here, we describe the generation of frFAST (far-red Fluorescence Activating and absorption Shifting Tag), a 14-kDa monomeric protein that forms a bright far-red fluorescent assembly with (4-hydroxy-3-methoxy-phenyl)allylidene rhodanine (HPAR-3OM). As HPAR-3OM is essentially non-fluorescent in solution and in cells, frFAST can be imaged with high contrast in presence of free HPAR-3OM, which allowed the rapid and efficient imaging of frFAST fusions in live cells, zebrafish embryo/larvae, and chicken embryos. Beyond enabling the genetic encoding of far-red fluorescence, frFAST allowed the design of a far-red chemogenetic reporter of protein–protein interactions, demonstrating its great potential for the design of innovative far-red emitting biosensors.     

Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

Mechanical mixtures of Me (Ni, Pd) Ce oxides and silica-supported heteropolyacids: Role and optimal concentration of each active species in n-hexane isomerization

Catalytic properties of silica-supported heteropolyacids (HPA) in a mechanical mixture with reduced Me-Ce oxides (Me = Ni, Pd) in n-hexane isomerization are studied. The role of each component of the mixed oxides (Ce and, typically, Ni and Pd) and their optimum content has been illuminated: cerium is not only beneficial for eliminating or preventing coke deposition but is also effective for maintaining the Keggin structure of the highly-organized HPA during the reaction and probably allows a better dispersion of the second metal species. Nickel and palladium, present as Ni⁰ and Pd⁰, reinforce the activation of the alkane, which is difficult to obtain by means of a direct attack by an acid, and, thus, enhance noticeably the activity of the catalyst. The best mechanical mixtures are obtained with 30–70 wt % NiCeO-HPW/SiO₂ and 50–50 wt % Pd_0.1CeO-HPW/SiO₂. These mixtures have the highest efficiency for a Ni/(Ni + W) atomic ratio of 0.66 and a Pd/(Pd + W) ratio of 0.40, respectively. Finally, the conversion of n-hexane is in the order HPW > HSiW > HBW, which seems to be consistent with the order of their acid strength as per the literature, but the isomerization selectivity appears to be slightly higher on HSiW. Published in Russian in Kinetika i Kataliz, 2006, Vol. 47, No. 1, pp. 24–28. The text was submitted by the authors in English.     

A short proof for a generalization of Vizing's theorem

For a simple graph of maximum degree Δ, it is always possible to color the edges with Δ + 1 colors (Vizing); furthermore, if the set of vertices of maximum degree is independent, Δ colors suffice (Fournier). In this article, we give a short constructive proof of an extension of these results to multigraphs. Instead of considering several color interchanges along alternating chains (Vizing, Gupta), using counting arguments (Ehrenfeucht, Faber, Kierstead), or improving nonvalid colorings with Fournier's Lemma, the method of proof consists of using one single easy transformation, called “sequential recoloring”, to augment a partial k-coloring of the edges.     

Study of the spontaneous formation of organic layers on carbon and metal surfaces from diazonium salts

This study investigates the spontaneous grafting of different para-substituted phenyl groups on carbon and metallic surfaces from diazonium salts solutions. Glassy carbon, nickel, zinc and iron plates were allowed to react with an acetonitrile solution of aryldiazonium tetrafluoroborate salt by simple dipping. The surfaces were characterized before and after their immersion by XPS and AFM to evidence the formation of a coating on the different materials. The results are indicative of the presence of substituted phenyl groups on all the investigated surfaces. This study also aims at correlating grafting efficiency with metal reactivities and diazonium salt electronic properties by means of AFM and FT-IRRAS. For this purpose, zinc and nickel were chosen due to their opposite reducing properties and two diazonium salts were selected with electron-donor or -withdrawing para-substituents. The results tend to indicate that redox properties of both partners (diazonium + metal) are of prime importance for grafting to occur.     

An efficient phosphine-free palladium coupling for the synthesis of new 2-arylbenzo[b]thiophenes

Straightforward and rapid access to 2-arylbenzo[b]thiophenes has been developed. It involved a catalytic coupling of 3-activated benzo[b]thiophenes with several aryl halides in the presence of a phosphine-free palladium system. In case of fragile functional groups such as aldehydes, a quaternary ammonium was used as an additive as with the other substrates, the coupling performed better and faster in the presence of a crown ether, the best one being DCH-18-C-6, with good yields and low reaction times. This method would provide a direct access to novel structures of biological interest.     

Rate of Convergence of a Stochastic Particle System for the Smoluchowski Coagulation Equation

By continuing the probabilistic approach of Deaconu et al. (2001), we derive a stochastic particle approximation for the Smoluchowski coagulation equations. A convergence result for this model is obtained. Under quite stringent hypothesis we obtain a central limit theorem associated with our convergence. In spite of these restrictive technical assumptions, the rate of convergence result is interesting because it is the first obtained in this direction and seems to hold numerically under weaker hypothesis. This result answers a question closely connected to the Open Problem 16 formulated by Aldous (1999).