Stereo- and Regiochemical Effect of N,N-Dialkylamide Extractants on the Speciation of Pu Complexes

The relationship between extractant stereochemistry and their extraction performance has only poorly been established. In order to address a part of this concern, we investigated the Pu(IV) liquid-liquid extraction (LLE) by using the N,N-di-(2-ethylhexyl)butyramide (DEHBA), as well as those of its position isomers. DEHBA (ββ-isomer) and N-(2-ethylhexyl)-N-(oct-3-yl)butyramide (EHOBA or αβ-isomer) were synthesized as a mixture of stereoisomer or stereoenriched (R,S)- and (S,S)-diastereoisomers, and were all assessed for Pu^IV LLE. The results showed that both the position and the stereoisomerism of the aliphatic substituents affect Pu^IV complexation and extraction. We found that Pu extraction is lowered by factor 2 to 4 when the ethyl branching group is closer to the complexing site. UV-vis spectroscopy showed that this extraction decrease was affected by steric hindrance inducing a deprivation of Pu inner sphere complex. Effect of stereoisomerism is highlighted for branching closer to the complexing site (α-position). Enantiopure DEHBA stereoisomers provided similar Pu extraction, whereas a slight decrease could be noticed for the more cluttered stereoenriched (αβ)-isomers, which was also concomitant with a smaller population of inner sphere complex. In contrast, the stereoisomers mixture led to a strong decrease of Pu extraction because of an antagonistic association in the mixed complexes.     

One-pot preparation of 2-(alkyl)arylbenzoselenazoles from the corresponding N-(acetyl)benzoyl-2-iodoanilines via a microwave-assisted methodology

We report here the first example of a one-pot synthesis of 2-(alkyl)arylbenzoselenazoles from N-(acetyl)benzoyl-2-iodoanilines. The reaction was carried out in the presence of Woollins’ reagent under microwave irradiation and resulted in moderate to good yields.     

Easy and efficient selenocyanation of imidazoheterocycles using triselenodicyanide

The regioselective selenocyanation of imidazoheterocycles using triselenodicyanide at room temperature is reported. The electrophilic aromatic substitution of a broad range of substrates is promoted by the triselenodicyanide obtained by oxidative coupling of malononitrile and selenium dioxide, under an air atmosphere. The major advantages of the presented method are an easy set-up, excellent yields, short reaction times, use of odorless and inexpensive reagents and easy purification of the final products.     

Cycle-maximal triangle-free graphs

We conjecture that the balanced complete bipartite graph _{K⌊n/2⌋,⌈n/2⌉}$K_{\lfloor n/2\rfloor ,\lceil n/2\rceil }$ contains more cycles than any other n$n$-vertex triangle-free graph, and we make some progress toward proving this. We give equivalent conditions for cycle-maximal triangle-free graphs; show bounds on the numbers of cycles in graphs depending on numbers of vertices and edges, girth, and homomorphisms to small fixed graphs; and use the bounds to show that among regular graphs, the conjecture holds. We also consider graphs that are close to being regular, with the minimum and maximum degrees differing by at most a positive integer k$k$. For k=1$k=1$, we show that any such counterexamples have n≤91$n\le 91$ and are not homomorphic to _C5$C_5$; and for any fixed k$k$ there exists a finite upper bound on the number of vertices in a counterexample. Finally, we describe an algorithm for efficiently computing the matrix permanent (a #P$\#P$-complete problem in general) in a special case used by our bounds.     

Influence of the aspect ratio on boiling flows in rectangular mini-channels

This article presents experiments conducted with two single rectangular mini-channels of same hydraulic diameter (1.4 mm) and different aspect ratios for conditions of horizontal boiling flow. The Forane® 365 HX used was subcooled (ΔT_sub = 15 °C) for all the boiling curves presented in the paper. Local heat transfer coefficients were measured for heat flux ranging from 25 to 62 kW m⁻² and mass flux from 200 kg m⁻² s⁻¹ to 400 kg m⁻² s⁻¹. The boiling flows were observed with two different cameras (depending on the flow velocity) through a visualization window. The flow patterns in the two channels were compared for similar conditions. The results show that the boiling heat transfer coefficient and the pressure drop values are different for the two single mini-channels. For low heat flux condition, the channel with lowest aspect ratio (H/W = 0.143) has a higher heat transfer coefficient. On the other hand, for high heat flux condition, the opposite situation occurs, namely the heat transfer coefficient becomes higher for the channel with highest aspect ratio (H/W = 0.43). This is probably due to the earlier onset of dryout in the channel with lowest aspect ratio. For the two cases of heating, the pressure drop for the two-phase flow remains lower for the channel with lowest aspect ratio. These results show that the aspect ratio plays a substantial role for boiling flows in rectangular channels. As for single-phase flows, the heat transfer characteristics are significantly influenced (even though the hydraulic diameter remains the same) by this parameter.     

A Bis(pyridine N‐oxide) Analogue of DOTA: Relaxometric Properties of the GdIII Complex and Efficient Sensitization of Visible and NIR‐Emitting Lanthanide(III) Cations Including PrIII and HoIII

We report the synthesis of a cyclen‐based ligand (4,10‐bis[(1‐oxidopyridin‐2‐yl)methyl]‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid= L1 ) containing two acetate and two 2‐methylpyridine N‐oxide arms anchored on the nitrogen atoms of the cyclen platform, which has been designed for stable complexation of lanthanide(III) ions in aqueous solution. Relaxometric studies suggest that the thermodynamic stability and kinetic inertness of the Gd^III complex may be sufficient for biological applications. A detailed structural study of the complexes by ¹H NMR spectroscopy and DFT calculations indicates that they adopt an anti‐Δ(λλλλ) conformation in aqueous solution, that is, an anti‐square antiprismatic (anti‐SAP) isomeric form, as demonstrated by analysis of the ¹H NMR paramagnetic shifts induced by Yb^III. The water‐exchange rate of the Gd^III complex is ${k{{298\hfill \atop {\rm ex}\hfill}}}$ =6.7×10⁶ s^?1, about a quarter of that for the mono‐oxidopyridine analogue, but still about 50 % higher than the ${k{{298\hfill \atop {\rm ex}\hfill}}}$ of GdDOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid). The 2‐methylpyridine N‐oxide chromophores can be used to sensitize a wide range of Ln^III ions emitting in both the visible (Eu^III and Tb^III) and NIR (Pr^III, Nd^III, Ho^III, Yb^III) spectral regions. The emission quantum yield determined for the Yb^III complex (${Q{{{\rm L}\hfill \atop {\rm Yb}\hfill}}}$ =7.3(1)×10^?3) is among the highest ever reported for complexes of this metal ion in aqueous solution. The sensitization ability of the ligand, together with the spectroscopic and relaxometric properties of its complexes, constitute a useful step forward on the way to efficient dual probes for optical imaging (OI) and MRI.     

Syntheses of nucleosides with 2′-spirolactam and 2′-spiropyrrolidine moieties as potential inhibitors of hepatitis C virus NS5B polymerase

To discover novel nucleosides as potential antiviral agents, 2′-spirolactam and 2′-spiropyrrolidine-containing nucleoside analogs were envisioned. Efficient synthetic routes were developed with an epoxide opening as the key step to establish the quaternary center at the 2′ position, leading to the design and synthesis of uridine analogs 8 and 21, prodrugs 13–16, and cytidine analog 11.     

Syntheses of 4′-spirocyclic phosphono-nucleosides as potential inhibitors of hepatitis C virus NS5B polymerase

To discover novel nucleosides as potential antiviral agents, 4′-spirocyclic phosphono-nucleosides were designed to mimic the monophosphate of R-1479, a known nucleoside inhibitor of HCV NS5B. Bypassing the first kinase step to nucleoside monophosphate is viewed as advantageous since this phosphorylation is often observed as the rate-limiting transformation to the active NTP for many nucleosides. Efficient synthetic routes were developed with a triphenylphosphine–iodine cyclization reaction as the key step to form the tetrahydrofuran 4′-spirocycle. The desired 4′-spirocyclic phosphono-cytidine analogs 12a, 12b, and 16 were prepared in 11 steps.