Regioselective Lewis acid-mediated [1,3] rearrangement of allylvinyl ethers

[reaction: see text]. Aluminum and copper Lewis acids were implemented to effect a regioselective [1,3] rearrangement of allylvinyl ethers in moderate to good yields. The use of trisubstituted alkenes leads to depressed levels of Claisen products.     

Novel coordination polymers and structural systematics in the hydrothermal M,M' trans-3(-3-pyridyl)acrylic acid system

The bifunctional ligand trans-3-(3-pyridyl)acrylic acid has been utilized to promote the formation of a novel hetero-metallic [Cu3(C8H6NO2)6Nd2(NO3)6] (1) and two homometallic: [Nd(C8H6NO2)3H2O] (2) and [Cu(C8H6NO2)2] x H2O (3) metal organic framework (MOF) materials. The philosophy here is that a mixture of hard (Nd3+) and softer metal cations will show preference for the carboxylic and pyridyl functional groups, respectively. As such, a 3-D topology 1 has emerged as a stable, heterometallic structure. Efforts to explore structural systematics in this system have led to the synthesis of homometallic end members and hence the formation of a 2-D coordination polymer 2, and a 1-D coordination polymer 3. Presented is an analysis of the effect of a second metal centre on coordination environment, overall structure formation, thermal and luminescence properties.     

Quantum simulations of the structure and binding of glycopeptide antibiotic aglycons to cell wall analogues

The recent rise of vancomycin-resistant enterococci (VRE) and vancomycin-resistant Staphylococcus aureus (VRSA) has given new impetus to the study of the binding between glycopeptide antibiotics and bacterial cell wall termini. Here, we report on an extensive first principles investigation of the binding of vancomycin, avoparcin, teicoplanin, and ristocetin aglycons with dipetides, Ac-d-Ala-X, where X = d-Lac and d-Ser (characteristic of VREs) and X = d-Ala, Gly (characteristic of non-VREs), and a model "methylated d-Ala" CH(2)CH(CH(3))COO(-), in liquid as well as gas phase. The gas-phase ordering of the binding, from strongest to weakest, is Gly, d-Ala, d-Ser, CH(2)CH(CH(3))COO(-), and d-Lac. Calculations show that the order of the Gly and d-Ala binding is reversed in solution. The results are in good agreement with recent experimental findings.     

Anisotropic metal nanoparticles: Synthesis, assembly, and optical applications

This feature article highlights work from the authors' laboratories on the synthesis, assembly, reactivity, and optical applications of metallic nanoparticles of nonspherical shape, especially nanorods. The synthesis is a seed-mediated growth procedure, in which metal salts are reduced initially with a strong reducing agent, in water, to produce approximately 4 nm seed particles. Subsequent reduction of more metal salt with a weak reducing agent, in the presence of structure-directing additives, leads to the controlled formation of nanorods of specified aspect ratio and can also yield other shapes of nanoparticles (stars, tetrapods, blocks, cubes, etc.). Variations in reaction conditions and crystallographic analysis of gold nanorods have led to insight into the growth mechanism of these materials. Assembly of nanorods can be driven by simple evaporation from solution or by rational design with molecular-scale connectors. Short nanorods appear to be more chemically reactive than long nanorods. Finally, optical applications in sensing and imaging, which take advantage of the visible light absorption and scattering properties of the nanorods, are discussed.     

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.     

Microwave transmission through a single subwavelength annular aperture in a metal plate

The resonant transmission of a small annular aperture, with a diameter much smaller than the radiation wavelength, in a thin metal plate is studied at microwave frequencies. It transpires that such an annular aperture supports several resonant guided modes, including those that are not quantized in the azimuthal direction. Such modes have resonant frequencies that are largely independent of the diameter of the annular aperture, thus being supported by annular apertures that tend to zero radius. The transmittance of such a structure at microwave frequencies is detailed and compared with the predictions of a finite element method model.     

Across-ear interference from parametrically degraded synthetic speech signals in a dichotic cocktail-party listening task

Recent results have shown that listeners attending to the quieter of two speech signals in one ear (the target ear) are highly susceptible to interference from normal or time-reversed speech signals presented in the unattended ear. However, speech-shaped noise signals have little impact on the segregation of speech in the opposite ear. This suggests that there is a fundamental difference between the across-ear interference effects of speech and nonspeech signals. In this experiment, the intelligibility and contralateral-ear masking characteristics of three synthetic speech signals with parametrically adjustable speech-like properties were examined: (1) a modulated noise-band (MNB) speech signal composed of fixed-frequency bands of envelope-modulated noise; (2) a modulated sine-band (MSB) speech signal composed of fixed-frequency amplitude-modulated sinewaves; and (3) a "sinewave speech" signal composed of sine waves tracking the first four formants of speech. In all three cases, a systematic decrease in performance in the two-talker target-ear listening task was found as the number of bands in the contralateral speech-like masker increased. These results suggest that speech-like fluctuations in the spectral envelope of a signal play an important role in determining the amount of across-ear interference that a signal will produce in a dichotic cocktail-party listening task.     

Background noise cancellation for improved acoustic detection of manatee vocalizations

The West Indian manatee (Trichechus manatus latirostris) has become endangered partly because of an increase in the number of collisions with boats. A device to alert boaters of the presence of manatees, so that a collision can be avoided, is desired. A practical implementation of the technology is dependent on the hydrophone spacing and range of detection. These parameters are primarily dependent on the manatee vocalization strength, the decay of the signal's strength with distance, and the background noise levels. An efficient method to extend the detection range by using background noise cancellation is proposed in this paper. An adaptive line enhancer (ALE) that can detect and track narrow band signals buried in broadband noise is implemented to cancel the background noise. The results indicate that the ALE algorithm can efficiently extract the manatee calls from the background noise. The improved signal-to-noise ratio of the signal can be used to extend the range of detection of manatee vocalizations and reduce the false alarm and missing detection rate in their natural habitat.     

Coherent reflection in a two-dimensional cochlea: Short-wave versus long-wave scattering in the generation of reflection-source otoacoustic emissions

The theory of coherent reflection filtering explains the empirical form of the cochlear reflectance by showing how it emerges from the coherent "backscattering" of forward-traveling waves by impedance perturbations in the mechanics of the cochlear partition. Since the theory was developed using the one-dimensional (1-D) transmission-line model of the cochlea, an obvious logical shortcoming is the failure of the long-wavelength approximation near the peak of the traveling wave, where coherent backscattering is purported to occur. Indeed, existing theory suggests that wave reflection may be strongly suppressed in the short-wave regime. To understand how short-wave behavior near the peak modifies the predictions of the long-wave theory, this paper solves the scattering problem in the 2-D cochlear model. The 2-D problem is reduced to a 1-D wave equation and the solution expressed as an infinite series in which successive terms arise via multiple scattering within the cochlea. The cochlear reflectance is computed in response-matched models constructed by solving the inverse problem to control for variations in mechanical tuning among models of different heights and dimensionality. Reflection from the peak region is significantly enhanced by the short-wave hydrodynamics, but other conclusions of the 1-D analysis--such as the predicted relation between emission group delay and the wavelength of the traveling wave--carry over with only minor modifications. The results illustrate the important role of passive hydromechanical effects in shaping otoacoustic emissions and cochlear tuning.     

Gold nanoshell bioconjugates for molecular imaging in living cells

Advances in scattering-based optical imaging technologies offer a new approach to noninvasive point-of-care detection, diagnosis, and monitoring of cancer. Emerging photonics technologies provide a cost-effective means to image tissue in vivo with high resolution in real time. Advancing the clinical potential of these imaging strategies requires the development of optical contrast agents targeted to specific molecular signatures of disease. We describe the use of a novel class of contrast agents based on nanoshell bioconjugates for molecular imaging in living cells. Nanoshells offer significant advantages over conventional imaging probes including continuous and broad wavelength tunability, far greater scattering and absorption coefficients, increased chemical stability, and improved biocompatibility. We show that nanoshell bioconjugates can be used to effectively target and image human epidermal growth factor receptor 2 (HER2), a clinically relevant biomarker, in live human breast carcinoma cells.