Macrocyclic Cyclopropenes by Highly Enantioselective Intramolecular Addition of Metal Carbenes to Alkynes

The intramolecular addition of a diazo ester group to a triple bond in the presence of chiral dirhodium(II ) carboxamidate catalysts gives macrocyclic lactones with a fused cycloproprene ring [Eq. (a)]. This efficient reaction is characterized by high enantiocontrol (up to 98% ee) and chemoselectivity.     

Combining selection valve and mixing chamber for nanoflow gradient generation: Toward developing a liquid chromatography cartridge coupled with mass spectrometer for protein and peptide analysis

Toward developing a micro HPLC cartridge, we have recently built a high-pressure electroosmotic pump (EOP). However, we do not recommend people to use this pump to deliver an organic solvent directly, because it often makes the pump rate unstable. We have experimented several approaches to address this issue, but none of them are satisfactory. Here, we develop an innovative approach to address this issue. We first create an abruption (a dead-volume) within a fluid conduit. We then utilize an EOP to withdraw, via a selection valve, a train of eluent solutions having decreasing eluting power into the fluid conduit. When these solutions are further aspirated through the dead-volume, these solutions are partially mixed, smoothening concentration transitions between two adjacent eluent solutions. As these solutions are pushed back, through the dead-volume again, a smooth gradient profile is formed. In this work, we characterize this scheme for gradient formation, and we incorporate this approach with a high-pressure EOP, a nanoliter injection valve, and a capillary column, yielding a micro HPLC system. We then couple this micro HPLC with an electrospray ionization – mass spectrometer for peptide and protein separations and identifications.     

Photomechanical effects in liquid crystal polymer networks prepared with m‐fluoroazobenzene

The photomechanical response and photochemistry of a conventional, unsubstituted azobenzene‐functionalized liquid crystalline polymer network (azo‐LCN) is contrasted to that of an analogous material prepared with meta‐fluorinated azobenzene chromophores. The polydomain azo‐LCN materials exhibit nearly identical thermomechanical and optical properties. Photomechanical characterization indicates that the fluorination of the azobenzene chromophore reduces the deflection of cantilevers composed of the materials by 50%, which spectroscopic analysis reveals is due to a reduction in the ability of this material to isomerize and potentially reorient. This work is further confirmation that the underlying photochemistry of azobenzene is a primary contributor to the generation of photomechanical work in these materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 876–882     

A correlation for burn time of aluminum particles in the transition regime

A study of the combustion times for aluminum particles in the size range of 3–11 μm with oxygen, carbon dioxide, and water vapor oxidizers at high temperatures (>2400 K), high pressures (4–25 atm), and oxidizer composition (15–70% by volume in inert diluent) in a heterogeneous shock tube has generated a correlation valid in the transition regime. The deviation from diffusion limited behavior and burn times that could otherwise be accurately predicted by the widely accepted Beckstead correlation is seen, for example, in particles below 20 μm, and is evidenced by the lowering of the diameter dependence on the burn time, a dependence on pressure, and a reversal of the relative oxidizer strengths of carbon dioxide and water vapor. The strong dependence on temperature of burn time that is seen in nano-Al is not observed in these micron-sized particles. The burning rates of aluminum in these oxidizers can be added to predict an overall mixture burnout time adequately. This correlation should extend the ability of modelers to predict combustion rates of particles in solid rocket motor environments down to particle diameters of a few microns.     

Tetrathiafulvalene Porphyrins

Four tetrathiafulvalene (TTF)‐annulated porphyrins 1 – 4 were synthesized and characterized. All contain a tetraphenylporphyrin (TPP) core onto which four, two, or one TTF subunits were annulated. Absorption and fluorescence spectroscopic studies together with electrochemical investigations reveal that interactions between the porphyrin system and the annulated TTF units take place in solution. The annulation of one or more TTF units to the porphyrin core has a profound effect on the reduction potentials associated with this latter framework, with positive shifts in the range of 0.105 to 0.355 V and 0.200 to 0.370 V for the first and second reduction potential, respectively, compared to the corresponding processes in the model compound TPP, 18 . The redox potentials for the first oxidation of the TTF units are considerably shifted in 4 (ΔE_ox¹=+0.285 V) and 2 (ΔE_ox¹=?0.140 V), whereas for 1 and 3 these potentials remain within the region expected for a normal TTF unit. Considerable changes in the second oxidation potential associated with the TTF subunits were seen for 2 (ΔE_ox¹=?0.085) and 3 (ΔE_ox¹=?0.175). The emission spectra of 1 – 4 revealed that the porphyrin fluorescence is almost quenched in the neutral state of the TTF‐annulated porphyrins, a finding that is consistent with substantial electron transfer taking place from the TTF subunits to the porphyrin core. Oxidation of the TTF unit(s) (TTF→TTF^.+) present in 1 – 4 leads to the emission intensity being restored.     

Tunable columnar mesophases utilizing C2 symmetric aromatic donor-acceptor complexes

Derivatives of relatively electron rich 1,5-dialkoxynaphthalene (Dan) donors and relatively electron deficient 1,4,5,8-naphthalenetetracarboxylic diimide (Ndi) acceptors have been exploited in the folding and self-assembly of a variety of complex molecular systems in solution. Here, we report the use of Dan and Ndi derivatives to direct assembly of extended columns with alternating face-centered stacked structure in the solid state. A variety of 1:1 Dan:Ndi mixtures produced mesophases that were found to be stable over temperature ranges extending up to 110 degrees C. Analysis of these mesophases indicates mixtures with soft/plastic crystal phases and a few mixtures with the thermodynamic properties of true liquid crystals, all composed of alternating donor-acceptor columns within. Importantly, a correspondence was found between the clearing and crystallization points of the mesophase mixtures and the melting/clearing points of the component Ndi and Dan units, respectively. This correspondence enables the predictable tuning of mesophase phase transition temperatures. The study of sterically hindered derivatives led to a set of mixtures in which a dramatic and sudden color change (deep red to yellow) was observed upon crystallization of the mesophase due to a phase separation of the component donor and acceptor units.     

Anticipating colloidal instabilities in cationic vesicle dispersions by measuring collective motions with dynamic light scattering

Vesicle dispersions are useful for many applications from medicinal to consumer products. However, using these dispersions requires some knowledge of and control over their colloidal properties. Measuring interparticle interactions between vesicles should allow framing the problem in terms of Smoluchowski kinetic models and consequently anticipating time-dependent aggregation and coalescence for the dispersions. However, this can be a difficult task for many complex mixtures. A primary goal of this paper is to show that it is possible to measure interparticle potential between small vesicles by measuring the concentration-dependent collective motion using dynamic light scattering. These measurements allow determination of the second virial coefficient for the dispersion, providing a convenient platform for summing all contributions to the interaction potential over all vesicle conformations, thus making the analysis of complex mixtures more tractable. As a verification of the approach, a comparison is made to dispersions in which the stability is governed solely by electrostatics, using existing techniques to anticipate instabilities. A second goal of this paper is to build a simple potential model in which the Smoluchowski model can be used to quantitatively anticipate the aggregation behavior of the small vesicle dispersion. Together, these observations constitute a convenient approach to anticipating the behavior of vesicle (and other) dispersions in complex mixtures.     

Electron transfer vs coordination chemistry: isomer-specific binding of HgII by an ortho-Wurster's thiacrown ether

Isomeric p- and o-phenylenediamine-containing macrocyclic hosts (Wurster's thiacrown ethers L1 and L2, respectively) were prepared and studied as Hg(II) ionophores. The distinct electrochemical properties of the two hosts allowed for the formation of a coordination compound with the ortho-Wurster's thiacrown ether but not the para isomer. In the latter case, the Hg(II) ion served as an oxidant in an electron-transfer reaction with the host. Solutions of the Hg(II) complex of L2 were studied by 13C NMR spectroscopy and cyclic voltammetry and revealed a strong interaction between the redox-active phenylenediamine subunit and the bound metal cation. An X-ray analysis confirmed the participation of the three macrocyclic S atoms and both phenylenediamine N atoms in the stabilization of the complex.