Noncovalent functionalization of single-walled carbon nanotubes with water-soluble porphyrins

We have employed water-soluble porphyrin molecules [meso-(tetrakis-4-sulfonatophenyl) porphine dihydrochloride] to solubilize single-walled carbon nanotubes (SWNTs), resulting in aqueous solutions that are stable for several weeks. The porphyrin-nanotube complexes have been characterized with absorption and fluorescence spectroscopy and with AFM. We find that the porphyrin/SWNT interaction is selective for the free base form, and that this interaction stabilizes the free base against protonation to the diacid. Under mildly acidic conditions nanotube-mediated J-aggregates form, which are unstable in solution and result in precipitation of the nanotubes over the course of a few days. Porphyrin-coated SWNTs can be precisely aligned on hydrophilic poly(dimethylsiloxane) (PDMS) surfaces by combing SWNT solution along a desired direction and then transferred to silicon substrates by stamping. Parallel SWNT patterns have been fabricated in this manner.     

Probing dipeptide trans/cis stereochemistry using pH control of thiopeptide analogues, and application to the PepT1 transporter

The stereochemistry of thiodipeptides of proline [e.g. Ala-Psi[CS-N]-Pro] can be controlled using pH, allowing the trans-preference for substrates of the peptide transporter PepT1 to be confirmed.     

Experimental evaluation of leaky least-mean-square algorithms for active noise reduction in communication headsets

An adaptive leaky normalized least-mean-square (NLMS) algorithm has been developed to optimize stability and performance of active noise cancellation systems. The research addresses LMS filter performance issues related to insufficient excitation, nonstationary noise fields, and time-varying signal-to-noise ratio. The adaptive leaky NLMS algorithm is based on a Lyapunov tuning approach in which three candidate algorithms, each of which is a function of the instantaneous measured reference input, measurement noise variance, and filter length, are shown to provide varying degrees of tradeoff between stability and noise reduction performance. Each algorithm is evaluated experimentally for reduction of low frequency noise in communication headsets, and stability and noise reduction performance are compared with that of traditional NLMS and fixed-leakage NLMS algorithms. Acoustic measurements are made in a specially designed acoustic test cell which is based on the original work of Ryan et al. ["Enclosure for low frequency assessment of active noise reducing circumaural headsets and hearing protection," Can. Acoust. 21, 19-20 (1993)] and which provides a highly controlled and uniform acoustic environment. The stability and performance of the active noise reduction system, including a prototype communication headset, are investigated for a variety of noise sources ranging from stationary tonal noise to highly nonstationary measured F-16 aircraft noise over a 20 dB dynamic range. Results demonstrate significant improvements in stability of Lyapunov-tuned LMS algorithms over traditional leaky or nonleaky normalized algorithms, while providing noise reduction performance equivalent to that of the NLMS algorithm for idealized noise fields.     

Ultramicroporous metal-organic framework based on 9,10-anthracenedicarboxylate for selective gas adsorption

An ultramicroporous metal-organic framework based on 9,10-anthracenedicarboxylate (PCN-13) has been synthesized and structurally characterized. The desolvated PCN-13 demonstrates selective adsorption of oxygen and hydrogen over nitrogen and carbon monoxide.     

Comparison of stable-isotope labeling with amino acids in cell culture and spectral counting for relative quantification of protein expression

Protein quantification is one of the principal goals of mass spectrometry (MS)-based proteomics, and many strategies exist to achieve it. Several approaches involve the incorporation of a stable-isotope label using either chemical derivatization, enzymatically catalyzed incorporation of (18)O, or metabolic labeling in a cell or tissue culture. These techniques can be cost or time prohibitive or not amenable to the biological system of interest. Label-free techniques including those utilizing integrated ion abundance and spectral counting offer an alternative to stable-isotope-based methodologies. Herein, we present the comparison of stable-isotope labeling of amino acids in cell culture (SILAC) with spectral counting for the quantification of human embryonic stem cells as they differentiate toward the trophectoderm at three time points. Our spectral counting experimental strategy resulted in the identification of 2641 protein groups across three time points with an average sequence coverage of 30.3%, of which 1837 could be quantified with more than five spectral counts. SILAC quantification was able to identify 1369 protein groups with an average coverage of 24.7%, of which 1027 could be quantified across all time points. Within this context we further explore the capacity of each strategy for proteome coverage, variation in quantification, and the relative sensitivity of each technique to the detection of change in relative protein expression.     

Concise routes to pyrazolo[1,5-a]pyridin-3-yl pyridazin-3-ones

Cycloaddition of pyridine N-imine with 6-alkyl-4-oxohex-5-ynoates followed by condensation with hydrazine provides concise access to pharmacologically active 6-(pyrazolo[1,5-a]pyridin-3-yl)pyridazinones. For the first time alkynyl heterocycles are also shown to be effective dipolarophiles for pyridine N-imine, and analogous compounds can be accessed directly in modest yields through the reaction of 6-(alkyn-1-yl)pyridazin-3-one derivatives.     

Hybrid feedforward-feedback active noise reduction for hearing protection and communication

A hybrid active noise reduction (ANR) architecture is presented and validated for a circumaural earcup and a communication earplug. The hybrid system combines source-independent feedback ANR with a Lyapunov-tuned leaky LMS filter (LyLMS) improving gain stability margins over feedforward ANR alone. In flat plate testing, the earcup demonstrates an overall C-weighted total noise reduction of 40 dB and 30-32 dB, respectively, for 50-800 Hz sum-of-tones noise and for aircraft or helicopter cockpit noise, improving low frequency (<100 Hz) performance by up to 15 dB over either control component acting individually. For the earplug, a filtered-X implementation of the LyLMS accommodates its nonconstant cancellation path gain. A fast time-domain identification method provides a high-fidelity, computationally efficient, infinite impulse response cancellation path model, which is used for both the filtered-X implementation and communication feedthrough. Insertion loss measurements made with a manikin show overall C-weighted total noise reduction provided by the ANR earplug of 46-48 dB for sum-of-tones 80-2000 Hz and 40-41 dB from 63 to 3000 Hz for UH-60 helicopter noise, with negligible degradation in attenuation during speech communication. For both hearing protectors, a stability metric improves by a factor of 2 to several orders of magnitude through hybrid ANR.