Bismuth trichloride–mediated cleavage of phenolic methoxymethyl ethers

A simple and efficient method for removal of phenolic methoxymethyl ethers in the presence of 30 mol% of bismuth trichloride in acetonitrile/water is described. Notable features of the cleavage protocol entail use of an ecofriendly bismuth reagent, ease of handling, low cost, operational simplicity, and good functional group compatibility. A number of structurally varied phenolic methoxymethyl ethers were cleaved in good to excellent yields.     

Reactivity of Diarylnitrenium Ions

Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar₂N⁺. Sequential H-atom abstraction reactions ensue. The first H-atom abstraction leads to intensely colored aminium radical cations, Ar₂NH^.+, some of which are quite stable. However, most undergo a second H-atom abstraction leading to ammonium ions, Ar₂NH₂⁺. In the absence of a ready source of H-atoms, a unique self-abstraction reaction occurs when Ar=Me₅C₆, leading to a novel iminium radical cation, Ar=N^.+Ar, which decays via a second self H-atom abstraction reaction to give a stable iminium ion, Ar=N⁺HAr. These products differ substantially from those derived via photochemically produced diarylnitrenium ions.     

The slow motion of two touching fluid spheres along their line of centers

The creeping motion along their line of centers of two fluid spheres in contact is analyzed. An exact solution is presented. Corrections to the Hadamard—Rybezynski equation are tabulated for various particle radii ratios and particle fluid to external fluid viscosity ratios. In the limit of infinite particle viscosity, these corrections are shown to agree with previous calculations for rigid spheres.     

The effect of hydrodynamic coupling on the thinning of a film between a drop and its homophase

The rate of thinning of a film trapped between a drop approaching its homophase according to a model incorporating hydrodynamic coupling is dramatically different from earlier, uncoupled models. Implications for film thinning of microflows analyzed in the preceding paper are here investigated using similar analytical methods to derive a nonautonomous, nonlinear evolution equation for the film thickness which has been solved numerically under a variety of conditions after asymptotic analytical behavior has been extracted. The applied force squeezing the film, together with the initial motion in the three phases, determines the rate of film thinning in a complicated manner through the coupling parameter R = (ρ_Aμ_A/ρ_Bμ_B)^{$\text{1}\text{2}$}. Experimental observations that normal drop circulation enhances thinning, whereas reversed drop circulation can cause thickening, are predicted theoretically for the first time. Films much more viscous than their surroundings are found to thin faster than the converse case, a conclusion at odds with offhand intuition but substantiated experimentally; both classes of systems behave differently, often qualitatively so, from predictions of hydrodynamically decoupled systems, and in particular film thinning rates are generally faster because of less resistance to drainage, although the limit of vanishing R does recover the special case of Reynolds' model. For short times, films are shown analytically to thin more rapidly if there is initially outward film motion and normal drop circulation, but with decreasing effectiveness as R increases, in contrast to the effect of R for intermediate and longer times; if there is initially inward film motion, thickening tendencies are enhanced by reverse drop circulation but with decreasing effectiveness as R increases. These and other detailed conclusions, most predicted theoretically for the first time, are not only in qualitative agreement with experimental observations, they are in quantitative agreement with available data.     

Queues in tandem with customer deadlines and retrials

We study queues in tandem with customer deadlines and retrials. We first consider a 2-queue Markovian system with blocking at the second queue, analyze it, and derive its stability condition. We then study a non-Markovian setting and derive the stability condition for an approximating diffusion, showing its similarity to the former condition. In the Markovian setting, we use probability generating functions and matrix analytic techniques. In the diffusion setting, we consider expectations of the first hitting times of compact sets.     

The Mercury (II) Catalyzed,One-Pot Oxidation of Terminal Alkynes by Sodium Perborate in Acetic Acid

A series of terminal alkynes has been reacted with sodium perborate and mercuric acetate catalyst in acetic acid to produce 1-acetoxyalkan-2-ones in good yield. The reaction constitutes a mild and convenient method for the oxidation of terminal triple bonds.     

MVF Sensor Enables Analysis of Nucleic Acids with Stable Secondary Structures

One major challenge in nucleic acids analysis by hybridization probes is a compromise between the probe's tight binding and sequence‐selective recognition of nucleic acid targets folded into stable secondary structures. We have been developing a four‐way junction (4WJ)‐based sensor that consists of a universal stem‐loop (USL) probe immobilized on an electrode surface and two adaptor strands (M and F). The sensor was shown to be highly selective towards single base mismatches at room temperature, able to detect multiple targets using the same USL probe, and have improved ability to detect folded nucleic acids. However, some nucleic acid targets, including natural RNA, are folded into very stable secondary and tertiary structures, which may represent a challenge even for the 4WJ sensors. This work describes a new sensor, named MVF since it uses three probe stands M, V and F, which further improves the performance of 4WJ sensors with folded targets. The MVF sensor interrogating a 16S rRNA NASBA amplicon with calculated folding energy of ?32.82 kcal/mol has demonstrated 2.5‐fold improvement in a signal‐to‐background ratio in comparison with a 4WJ sensor lacking strand V. The proposed design can be used as a general strategy in the analysis of folded nucleic acids including natural RNA.