Isomeric effects on the self‐assembly of a plausible prebiotic nucleoside analogue: A theoretical study

The self‐assembly properties of N(9)‐(2,3‐dihydroxypropyl adenine) (DHPA), a plausible prebiotic nucleoside analogue of adenosine, were investigated using density functional theory. Two different isomers were considered, and it is found that while both isomers can form a variety of structures, including chains, one of them is also able to form cages and helixes. When these results were put in the context of substrate supported molecular self‐assembly, it is concluded that gas‐phase self‐assembly studies that consider isomer identity and composition not only can aid interpreting the experimental results, but also reveal structures that might be overlooked otherwise. In particular, this study suggest that a double‐helical structure made of DHPA molecules which could have implications in prebiotic chemistry and nanotechnology, is stable even at room temperature. For example electrical properties (energy gap of 4.52eV) and a giant permanent electrical dipole moment (49.22 Debye) were found in our larger double‐helical structure (3.7 nm) formed by 14 DHPA molecules. The former properties could be convenient for construction of organic dielectric‐based devices.     

The Revival of Enantioselective Perfluoroalkylation – Update of New Synthetic Approaches from 2015–2022

Over the last years, methods devoted to the synthesis of asymmetric molecules bearing a perfluoroalkylated chain have been limited in number. Among them, only a few can be used on a large variety of scaffolds. This microreview aims at summarizing these recent advances in enantioselective perfluoroalkylation (−CF₃, −CF₂H, −C_nF_2n+1) and highlights the need for new enantioselective methods to easily synthesize chiral fluorinated molecules which would be useful for the pharmaceutical and agrochemical industries. Some perspectives are also mentioned.     

First measurements of the HCFC-142b trend from atmospheric chemistry experiment (ACE) solar occultation spectra

The first measurement of the HCFC-142b (CH₃CClF₂) trend near the tropopause has been derived from volume mixing ratio (VMR) measurements at northern and southern hemisphere mid-latitudes for the 2004–2008 time period from spaceborne solar occultation observations recorded at 0.02 cm⁻¹ resolution with the ACE (atmospheric chemistry experiment) Fourier transform spectrometer. The HCFC-142b molecule is currently the third most abundant HCFC (hydrochlorofluorocarbon) in the atmosphere and ACE measurements over this time span show a continuous rise in its volume mixing ratio. Monthly average measurements at northern and southern hemisphere mid-latitudes have similar increase rates that are consistent with surface trend measurements for a similar time span. A mean northern hemisphere profile for the time span shows a near constant VMR at 8–20 km altitude range, consistent on average for the same time span with in situ results. The nearly constant vertical VMR profile also agrees with model predictions of a long lifetime in the lower atmosphere.     

Phase-sensitive optical low-coherence reflectometry technique applied to the characterization of photonic crystal fiber properties

Localized measurements of group-velocity dispersion and birefringence of photonic crystal fibers are achieved with a phase-sensitive optical low-coherence reflectometry technique. This technique is efficient for fiber samples no longer than 1 m. Theoretical simulations are in good agreement with experimental results. As a result, the stress-induced birefringence proves to be at most 1 order of magnitude below the geometrical-shape birefringence.     

Measures on the Splitting Subspaces of an Inner Product Space

Let S be an inner product space and let E(S) (resp. F(S)) be the orthocomplemented poset of all splitting (resp. orthogonally closed) subspaces of S. In this article we study the possible states/charges that E(S) can admit. We first prove that when S is an incomplete inner product space such that dim S/S < , then E(S) admits at least one state with a finite range. This is very much in contrast to states on F(S). We then go on showing that two-valued states can exist on E(S) not only in the case when E(S) consists of the complete/cocomplete subspaces of S. Finally we show that the well known result which states that every regular state on L(H) is necessarily -additive cannot be directly generalized for charges and we conclude by giving a sufficient condition for a regular charge on L(H) to be -additive.     

Une Conjecture de Lebesgue

Let A > 0 be an integer. The equation x⁵–y⁵ = Az⁵ wasfirst studied by Dirichlet and Lebesgue. Lebesgue conjecturedin 1843 that if A has no prime divisors of the form 10k+1, theequation has no solutions except the visible ones. Partial resultswere obtained by Lebesgue and by Terjanian in 1987. The purposeof the paper is to prove Lebesgue's conjecture. The main toolused is the method known as the elliptic Chabauty method.     

On the capacity of sets of divergence associated with the spherical partial integral operator

In this article, we study the pointwise convergence of the spherical partial integral operator when it is applied to functions with a certain amount of smoothness. In particular, for , , , we prove that -quasieverywhere on , where is such that almost everywhere. A weaker version of this result in the range as well as some related localisation principles are also obtained. For and , we construct a function such that diverges everywhere.

     

Nafion as cosurfactant: solubilization of nafion in water in the presence of Pluronics

Incorporation of Nafion to aqueous solutions of Pluronics adversely impacts micellization due to extensive Nafion/copolymer interactions. Light scattering and zeta potential measurements provide evidence for the formation of sizable and stable Nafion/copolymer complexes, in expense of the neat copolymer micelles. At high copolymer concentrations, the overall interaction diagram of Nafion/copolymer reflects the competitive action of the release of packing constraints due to micellar destabilization induced by Nafion on one hand and the gelator nature of the Nafion on the other. Measurements using a quartz crystal microbalance (QCM-D) show that aqueous solutions of Pluronics (even at very low concentration) can dissolve the Nafion coating on the crystal resonator, while typical low molecular weight ionic surfactants fail to induce similar effects. These studies demonstrate that complexation with this class of copolymers is a facile route to impart dispersibility to Nafion in aqueous environments that otherwise can be achieved through tedious and harsh treatments.