Cascade polycyclisations in natural product synthesis

The efficient, stereocontrolled construction of polycyclic ring systems has long presented a formidable challenge to synthetic chemists. Cascade reactions offer a 'quick fix'--building multiple rings in a single step--and often dramatically shorten a synthetic route. In this Emerging Area article, a selection of the most recent and impressive examples of applications of this tactic to natural product synthesis are discussed, which demonstrate the ambition and achievements of the modern synthetic chemist.     

Regioselective synthesis of 2,3,4- or 2,3,5-trisubstituted pyrroles via [3,3] or [1,3] rearrangements of O-vinyl oximes

The regioselective synthesis of 2,3,4- or 2,3,5-trisubstituted pyrroles has been achieved via [3,3] and [1,3] sigmatropic rearrangements of O-vinyl oximes, respectively. Iridium-catalyzed isomerization of easily prepared O-allyl oximes enables rapid access to O-vinyl oximes. The regioselectivity of pyrrole formation can be controlled by either the identity of the α-substituent or through the addition of an amine base. When enolization is favored, a [3,3] rearrangement followed by a Paal-Knorr cyclization provides a 2,3,4-trisubstituted pyrrole; when enolization is disfavored, a [1,3] rearrangement occurs prior to enolization to produce a 2,3,5-trisubstituted pyrrole after cyclization. Optimization and scope of the O-allyl oxime isomerization and subsequent pyrrole formation are discussed and mechanistic pathways are proposed. Conditions are provided for selecting either the [3,3] rearrangement or the [1,3] rearrangement product with β-ester O-allyl oxime substrates.     

First-principles investigation of low energy E' center precursors in amorphous silica

We show that oxygen vacancies are not necessary for the formation of E' centers in amorphous SiO? and that a single O deficiency can lead to two charge traps. Employing molecular dynamics with a reactive potential and density functional theory, we generate an ensemble of stoichiometric and oxygen-deficient amorphous SiO? atomic structures and identify low-energy network defects. Three-coordinated Si atoms appear in several low-energy defects both in stoichiometric and O-deficient samples where, in addition to the neutral oxygen vacancy, they appear as isolated defects.     

Measuring vortex charge with a triangular aperture

A triangular aperture illuminated with a vortex beam creates a truncated lattice diffraction pattern that identifies the charge of the vortex. In this Letter, we demonstrate the measurement of vortex charge via this approach for vortex beams up to charge ±7. We also demonstrate the use of this technique for measuring femtosecond vortices and noninteger vortices, comparing these results with numerical modeling. It is shown that this technique is simple and reliable, but care must be taken when interpreting the results for the noninteger case.     

Study of the internal structure and small-scale instabilities in the dense Z pinch

High-resolution laser diagnostics at the wavelength of 266 nm were applied for the investigation of Z pinches at the 1-MA generator. The internal structure of the stagnated Z pinches was observed in unprecedented detail. A dense pinch with strong instabilities was seen inside the column of the trailing plasma. Kink instability, disruptions, and micropinches were seen at the peak of the x-ray pulse and later in time. The three-dimensional structure of the stagnated Z pinch depends on the initial wire-array configuration and implosion scenario. Small-scale density perturbations were found in the precursor plasma and in the stagnated Z pinch. Development of instabilities is in agreement with three-dimensional magnetohydrodynamic simulations.     

Measurement of the parity-violating longitudinal single-spin asymmetry for W± boson production in polarized proton-proton collisions at sqrt[s] = 500 GeV

We report the first measurement of the parity-violating single-spin asymmetries for midrapidity decay positrons and electrons from W+ and W- boson production in longitudinally polarized proton-proton collisions at sqrt[s] = 500 GeV by the STAR experiment at RHIC. The measured asymmetries, A(L)(W+) = -0.27 ± 0.10(stat.) ± 0.02(syst.) ± 0.03(norm.) and A(L)(W-) = 0.14 ± 0.19(stat.) ± 0.02(syst.) ± 0.01(norm.), are consistent with theory predictions, which are large and of opposite sign. These predictions are based on polarized quark and antiquark distribution functions constrained by polarized deep-inelastic scattering measurements.     

Chaotic spin-wave solitons in magnetic film feedback rings

Chaotic spin-wave solitons in magnetic film active feedback rings were observed for the first time. At some ring gain level, one observes the self-generation of a single spin-wave soliton pulse in the ring. When the pulse circulates in the ring, its amplitude varies chaotically with time. Numerical simulations based on a gain-loss nonlinear Schr?dinger equation reproduce the observed responses.     

Determining attenuation properties of interfering fast and slow ultrasonic waves in cancellous bone

Previous studies have shown that interference between fast waves and slow waves can lead to observed negative dispersion in cancellous bone. In this study, the effects of overlapping fast and slow waves on measurements of the apparent attenuation as a function of propagation distance are investigated along with methods of analysis used to determine the attenuation properties. Two methods are applied to simulated data that were generated based on experimentally acquired signals taken from a bovine specimen. The first method uses a time-domain approach that was dictated by constraints imposed by the partial overlap of fast and slow waves. The second method uses a frequency-domain log-spectral subtraction technique on the separated fast and slow waves. Applying the time-domain analysis to the broadband data yields apparent attenuation behavior that is larger in the early stages of propagation and decreases as the wave travels deeper. In contrast, performing frequency-domain analysis on the separated fast waves and slow waves results in attenuation coefficients that are independent of propagation distance. Results suggest that features arising from the analysis of overlapping two-mode data may represent an alternate explanation for the previously reported apparent dependence on propagation distance of the attenuation coefficient of cancellous bone.     

Ultrasonic anechoic chamber qualification: accounting for atmospheric absorption and transducer directivity

Qualifying an anechoic chamber for frequencies that extend into the ultrasonic range is necessary for research work involving airborne ultrasonic sound. The ANSI S12.55/ISO 3745 standard which covers anechoic chamber qualification does not extend into the ultrasonic frequency range, nor have issues pertinent to this frequency range been fully discussed in the literature. An increasing number of technologies employ ultrasound; hence the need for an ultrasonic anechoic chamber. This paper will specifically discuss the need to account for atmospheric absorption and issues pertaining to source transducer directivity by presenting some results for qualification of a chamber at Brigham Young University.     

Direct probing of micromechanical properties of hydrogen-bonded layer-by-layer microcapsule shells with different chemical compositions

The mechanical properties of hydrogen-bonded layer-by-layer (LbL) microcapsule shells constructed from tannic acid (TA) and poly(vinylpyrrolidone) (PVPON) components have been studied in both the dry and swollen states. In the dry state, the value of the elastic modulus was measured to be within 0.6-0.7 GPa, which is lower than the typical elastic modulus for electrostatically assembled LbL shells. Threefold swelling of the LbL shells in water results in a significant reduction of the elastic modulus to values well below 1 MPa, which is typical value seen for highly compliant gel materials. The increase of the molecular weight of the PVPON component from 55 to 1300 kDa promotes chain entanglements and causes a stiffening of the LbL shells with a more than 2-fold increase in elastic modulus value. Moreover, adding a polyethylenimine prime layer to the LbL shell affects the growth of hydrogen-bonded multilayers which consequently results in dramatically stiffer, thicker, and rougher LbL shells with the elastic modulus increasing by more than an order of magnitude, up to 4.3 MPa. An alternation of the elastic properties of very compliant hydrogen-bonded shells by variation of molecular weight is a characteristic feature of weakly bonded LbL shells. Such an ability to alter the elastic modulus in a wide range is critically important for the design of highly compliant microcapsules with tunable mechanical stability, loading ability, and permeability.