A Spirocyclohexyl Nitroxide Amino Acid Spin Label for Pulsed EPR Spectroscopy Distance Measurements

Site‐directed spin labeling and EPR spectroscopy offer accurate, sensitive tools for the characterization of structure and function of macromolecules and their assemblies. A new rigid spin label, spirocyclohexyl nitroxide α‐amino acid and its N‐(9‐fluorenylmethoxycarbonyl) derivative, have been synthesized, which exhibit slow enough spin‐echo dephasing to permit accurate distance measurements by pulsed EPR spectroscopy at temperatures up to 125 K in 1:1 water/glycerol and at higher temperatures in matrices with higher glass transition temperatures. Distance measurements in the liquid nitrogen temperature range are less expensive than those that require liquid helium, which will greatly facilitate applications of pulsed EPR spectroscopy to the study of structure and conformation of peptides and proteins.     

Cubanes: Starting Materials for the Chemistry of the 1990s and the New Century

The study of non-natural products has led to a broad understanding of bonding and reactivity in organic chemistry. Many times, compounds thought impossible have been realized in the course of such studies. Cubane, a landmark in the world of “impossible” compounds, has been found to have a rich chemistry, full of the unexpected. The recent renaissance of cubane chemistry, triggered by potential applications of the system to the production of high-energy fuels and the like, has led to many discoveries including the first methods for systematic substitution on strained, saturated systems and a new process for the metalation of arenes, ortho magnesiation. Reactive intermediates with exceptional bonding parameters have been uncovered and characterized including 1(9)-homocubene, the most twisted olefin; cubene, the most pyramidalized olefin; cubyl cation, once the “least likely” cation; cubylmethyl radical, a saturated radical that rearranges on the picosecond timescale; and many other extraordinary species. There is certainly good reason to believe that future work in the cubane arena will be at least as productive (probably more so), and that it will help develop a deeper understanding of chemistry.     

The Asymptotic Distribution of Singular-Values with Applications to Canonical Correlations and Correspondence Analysis

Let X_n, n = 1, 2, ... be a sequence of p × q random matrices, p ≥ q. Assume that for a fixed p × q matrix B and a sequence of constants b_n → ∞, the random matrix b_n(X_n − B) converges in distribution to Z. Let ψ(X_n) denote the q-vector of singular values of X_n. Under these assumptions, the limiting distribution of b_n (ψ(X_n) − ψ(B)) is characterized as a function of B and of the limit matrix Z. Applications to canonical correlations and to correspondence analysis are given.     

A correction method for measuring turbulence kinetic energy dissipation rate by PIV

The accuracy of turbulent kinetic energy (TKE) dissipation rate measured by PIV is studied. The critical issue for PIV-based dissipation measurements is the strong dependency on the spatial resolution, Δx, as reported by Saarenrinne and Piirto (Exp Fluids Suppl:S300–S307, 2000). When the PIV spacing is larger than the Kolmogorov scale, η, the dissipation is underestimated because the small scale fluctuations are filtered. For the case of Δx smaller than the Kolmogorov scale, the error rapidly increases due to noise. We introduce a correction method to eliminate the dominant error for the small Δx case. The correction method is validated by using a novel PIV benchmark, random Oseen vortices synthetic image test (ROST), in which quasi-turbulence is generated by randomly superposing multiple Oseen vortices. The error of the measured dissipation can be more than 1,000% of the analytical dissipation for the small Δx case, while the dissipation rate is underestimated for the large Δx case. Though the correction method does not correct the underestimate due to the low resolution, the dissipation was accurately obtained within a few percent of the true value by using the correction method for the optimal resolution of η/10 < Δx < η/2.     

Long-lived charge carrier generation in ordered films of a covalent perylenediimide–diketopyrrolopyrrole–perylenediimide molecule

The photophysics of a covalently linked perylenediimide–diketopyrrolopyrrole–perylenediimide acceptor–donor–acceptor molecule (PDI–DPP–PDI, 1) were investigated and found to be markedly different in solution versus in unannealed and solvent annealed films. Photoexcitation of 1 in toluene results in quantitative charge separation in τ = 3.1 ± 0.2 ps, with charge recombination in τ = 340 ± 10 ps, while in unannealed/disordered films of 1, charge separation occurs in τ < 250 fs, while charge recombination displays a multiexponential decay in ∼6 ns. The absence of long-lived, charge separation in the disordered film suggests that few free charge carriers are generated. In contrast, upon CH₂Cl₂ vapor annealing films of 1, grazing-incidence X-ray scattering shows that the molecules form a more ordered structure. Photoexcitation of the ordered films results in initial formation of a spin-correlated radical ion pair (electron–hole pair) as indicated by magnetic field effects on the formation of free charge carriers which live for ∼4 μs. This result has significant implications for the design of organic solar cells based on covalent donor–acceptor systems and shows that long-lived, charge-separated states can be achieved by controlling intramolecular charge separation dynamics in well-ordered systems.     

Calix[4]arene nitroxide tetraradical and octaradical

1,3-Alternate calix[4]arene with para-phenylene spacers connecting nitroxide monoradicals and high-spin (S = 1) diradicals provides tetraradical and octaradical scaffolds that possess conformations with slow electron spin relaxation rates (1/T(1)). Such scaffolds may facilitate tuning of relaxation rates that are more favorable for MRI or DNP applications.