Sporolides A and B: structurally unprecedented halogenated macrolides from the marine actinomycete Salinispora tropica

[structure: see text] Analysis of the fermentation broth of a strain of the marine actinomycete Salinispora tropica has led to the isolation of two unprecedented macrolides, sporolides A (1) and B (2). The structures and absolute stereochemistries of both metabolites were elucidated using a combination of NMR spectroscopy and X-ray crystallography.     

Application of glycodiversification: expedient synthesis and antibacterial evaluation of a library of kanamycin B analogues

[reaction: see text] The expedient synthesis of a library of kanamycin B analogues is reported. The revealed SAR will guide future designs in developing kanamycin-type aminoglycoside antibiotics against drug-resistant bacteria.     

Building blocks for N-type molecular and polymeric electronics. Perfluoroalkyl- versus alkyl-functionalized oligothiophenes (nTs; n = 2-6). Systematic synthesis, spectroscopy, electrochemistry, and solid-state organization

The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) alpha,omega-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2-6), (ii) beta,beta'-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2-6), (iii) alpha,omega-dihexyl-nTs 3 (DH-nTs, n = 2-6), (iv) beta,beta'-dihexyl-nTs 4 (isoDH-nTs, n = 2-6), and (v) unsubstituted oligothiophenes 5 (alphanTs, n = 2-6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1-5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocarbon-substituted oligomers are also presented and compared. The combined analysis of these data indicates that fluorocarbon-substituted nT molecules strongly interact in the condensed state, with unit cell level phase separation between the aromatic core and fluorocarbon chains. Surprisingly, despite these strong intermolecular interactions, high solid-state fluorescence efficiencies are exhibited by the fluorinated derivatives. Insight into the solution molecular geometries and conformational behavior are obtained from analysis of optical and variable-temperature NMR spectra. Finally, cyclic voltammetry data offer a reliable picture of frontier MO energies, which, in combination with DFT computations, provide key information on relationships between oligothiophene substituent effects and electronic response properties.     

Synthesis of readily cleavable immobilized 1,10-phenanthroline resins

1,10-Phenanthroline is derivatized and ultimately immobilized on two different polystyrene/divinylbenzene solid supports using convenient methodology. All syntheses are amenable to semiautomatic processing and are scalable for high-throughput screening. A domino copper-catalyzed coupling-cyclization reaction is used to illustrate applicability in catalytic studies.     

All frame-spun knots are slice

Frame-spun knots are constructed by spinning a knot of lower dimension about a framed submanifold of . We show that all frame-spun knots are slice (null-cobordant).

     

A nonmusical paradigm for identifying absolute pitch possessors

The ability to identify and reproduce sounds of specific frequencies is remarkable and uncommon. The etiology and defining characteristics of this skill, absolute pitch (AP), have been very controversial. One theory suggests that AP requires a specific type of early musical training and that the ability to encode and remember tones depends on these learned musical associations. An alternate theory argues that AP may be strongly dependent on hereditary factors and relatively independent of musical experience. To date, it has been difficult to test these hypotheses because all previous paradigms for identifying AP have required subjects to employ knowledge of musical nomenclature. As such, these tests are insensitive to the possibility of discovering AP in either nonmusicians or musicians of non-Western training. Based on previous literature in pitch memory, a paradigm is presented that is intended to distinguish between AP possessors and nonpossessors independent of the subjects' musical experience. The efficacy of this method is then tested with 20 classically defined AP possessors and 22 nonpossessors. Data from these groups strongly support the validity of the paradigm. The use of a nonmusical paradigm to identify AP may facilitate research into many aspects of this phenomenon.     

Experimental implementation of an adiabatic quantum optimization algorithm

We report the realization of a nuclear magnetic resonance computer with three quantum bits that simulates an adiabatic quantum optimization algorithm. Adiabatic quantum algorithms offer new insight into how quantum resources can be used to solve hard problems. This experiment uses a particularly well-suited three quantum bit molecule and was made possible by introducing a technique that encodes general instances of the given optimization problem into an easily applicable Hamiltonian. Our results indicate an optimal run time of the adiabatic algorithm that agrees well with the prediction of a simple decoherence model.     

Polarization decorrelation in optical fibers with randomly varying elliptical birefringence

Polarization decorrelation in single-mode fibers with randomly varying elliptical birefringence is studied. It is found that the effects of ellipticity on the polarization decorrelation length depend on the relative sizes of the beat length and the autocorrelation length of the birefringence fluctuations in the fiber. However, the evolution of the differential group delay remains unaffected by ellipticity.     

Time course of loudness recalibration: implications for loudness enhancement

Loudness recalibration, the effect of a relatively loud 2500-Hz recalibrating tone on the loudness of a relatively soft 2500-Hz target tone, was measured as a function of the interstimulus interval (ISI) between them. The loudness of the target tone, assessed by a 500-Hz comparison tone, declined when the ISI equaled or exceeded about 200 ms and leveled off at an ISI of about 700 ms. Notably, the target tone's loudness did not change significantly at very short ISIs (< 150 ms). The latter result is incompatible with the literature reporting loudness enhancement in this time window, but is compatible with the suggestion made by Scharf, Buus, and Nieder [J. Acoust. Soc. Am. 112, 807-810 (2002)] that early measurements of enhancement were contaminated by the influence of the recalibrating tone on the comparison tone when the two shared the same frequency. In a second experiment the frequency of the comparison tone was changed to 2500 Hz and the results of a loudness enhancement paradigm was successfully predicted from the time course of recalibration obtained in experiment 1.     

To fold or to assemble?

We introduce a new class of foldable oligomers consisting of alternating rigid and flexible regions. The rigid segments overlap to give pi-stacked folded conformers whose formation is driven mostly by pi-pi molecular orbital overlaps. As the oligomer concentration increases, the folded molecular structures further self-assemble into larger nanostructures. The dynamic processes of folding and self-organization are monitored with absorption, fluorescence, and NMR spectroscopies. Our results show that folding dominates at low concentrations (< approximately 1 mM) and precedes self-assembly, which occurs over the initial concentration range of approximately 1-100 mM.