Electrochemical nitric oxide sensor preparation: a comparison of two electrochemical methods of electrode surface modification

Platinum electrodes modified with Mn(II) 5-(N-(8-pyrrole-yl-3,6-dioxa-1-aminooctane)phenylamide-10,15,20-trimethoxyphenylporphyrin (Mn(II)triOMeTCPPyP) using multi-sweep cyclic voltammetry and differential pulse amperometry were evaluated as electrocatalytic surfaces for the oxidation of nitric oxide. The electrodes modified using the pulse amperometric approach were more sensitive towards the detection of nitric oxide. The increased sensitivity led to the attainment of a wider linear dynamic range for the quantification of nitric oxide.     

Electric field modulation of galvanomagnetic properties of mesoscopic graphite

Electric field effect devices based on mesoscopic graphite are fabricated for galvanomagnetic measurements. Strong modulation of magnetoresistance and Hall resistance as a function of the gate voltage is observed as the sample thickness approaches the screening length. Electric field dependent Landau level formation is detected from Shubnikov-de Haas oscillations. The effective mass of electron and hole carriers has been measured from the temperature dependent behavior of these oscillations.     

Passive mode-locking by use of waveguide arrays

A novel mode-locking technique is presented in which the intensity-dependent spatial coupling dynamics of a waveguide array is used to achieve temporal mode-locking in a passive optical fiber laser. By use of the discrete, nearest-neighbor spatial coupling of the waveguide array, low-intensity light can be transferred to the neighboring waveguides and ejected (attenuated) from the laser cavity. In contrast, higher-intensity light is self-focused in the waveguide and remains largely unaffected. Numerical studies of this pulse shaping mechanism (intensity discrimination) show that using current waveguide arrays and standard optical fiber technology produces stable and robust mode-locked soliton-like pulses.     

Total absorption of an electromagnetic wave by an overdense plasma

We show both theoretically and experimentally that an electromagnetic wave can be totally absorbed by an overdense plasma when a subwavelength diffraction grating is placed in front of the plasma surface. The absorption is due to dissipation of surface plasma waves (plasmons polaritons) that have been resonantly excited by the evanescent component of the diffracted electromagnetic wave. The developed theoretical model allows one to determine the conditions for the total absorption.     

Effects of informational maskers within and across trials

The across-trial effect of maskers in conditions of informational masking was evaluated from performance on occasional trials in which the signal was presented alone. For 6 of 12 listeners participating in the study, a significant number of errors were obtained on signal-alone trials; in some cases equivalent to that signal+ masker trials. On immediately preceding trial blocks for which there were no intervening maskers, performance for these signals was perfect. The results indicate that informational maskers can have a significant effect on signal threshold, both within and across trials.     

Classification and identification of recorded and synthesized impact sounds by practiced listeners, musicians, and nonmusicians

Three experiments were conducted to test the viability of a low-parameter modal model for synthesizing impact sounds to be used in commercial and psychoacoustic research. The model was constrained to have four physically based parameters dictating the amplitude, frequency, and decay of modes. The values of these parameters were selected by ear to roughly match the recordings of ten different resonant objects suspended by hand and struck with different mallets. In experiment 1, neither 35 professional musicians nor 187 college undergraduates could identify which of the two matched sounds was the real recording with better than chance accuracy, though significantly better than chance performance was obtained when modal parameters were selected without the previously imposed physical constraints. In experiment 2, the undergraduates identified the source corresponding to the recorded and synthesized sounds with the same level of accuracy and largely the same pattern of errors. Finally, experiment 3 showed highly practiced listeners to be largely insensitive to changes in the acoustic waveform resulting from an increase in the number of free parameters used in the modal model beyond 3. The results suggest that low-parameter, modal models might be exploited meaningfully in many commercial and research applications involving human perception of impact sounds.     

Forced folding and structural analysis of metastable proteins

A significant fraction of the proteins encoded by the human and other genomes appears to be significantly unfolded in vitro. This will undoubtedly hamper attempts to characterize their structure by classical crystallographic or solution NMR methods. Here we show that encapsulation of a metastable protein within the restricted volume a reverse micelle can be used to force fold the protein and allow its characterization by modern methods of NMR spectroscopy. This may have significant utility in the context of structural proteomics. In addition, variation of the inner volume of the reverse micelle can be used to probe the character of the manifold of unfolded states.     

Structural determination of 5'-OH alpha-ribofuranoside modified cobalamins via 13C and DEPT NMR

A protocol for the rapid NMR characterization of cobalamin (vitamin B(12)) analogues with 5'-hydroxy-alpha-ribofuranoside modification is reported. The structure of cyanocobalamin in DMSO-d(6) has been assigned using COSY, NOESY, HSQC, and HMBC NMR methods. The robust precision of (13)C NMR assignments in DMSO-d(6) allows for the rapid structural determination of 5'-hydroxy-alpha-ribofuranosyl cyanocobalamin derivatives with solely 1-D (13)C and DEPT NMR spectra and only 10 mg of derivatized cobalamin. Using this method, the (13)C NMR resonances of four cobalamin analogues were determined with the most significant variance of (13)C chemical shifts occurring in the alpha-ribofuranoside ring. In DMSO-d(6), cobalamin concentrations greater than 30 mM can be achieved for an improved signal-to-noise ratio.     

Synthesis and crystallographic characterization of a ‘palladadehydrobenzo[19]annulene’

The trans-palladium bis(σ-acetylide) complex (Et₃P)₂Pd(C₃₀H₁₂) (2) was synthesized from hexane 4 in 77% yield via a simple three-step process. The X-ray crystal structure of 2 shows a strained and warped annulenic core upon insertion of the organometallic fragment. UV-vis data of the molecule suggest limited electronic delocalization throughout the metallacycle.     

Chiral Ru-based complexes for asymmetric olefin metathesis: enhancement of catalyst activity through steric and electronic modifications

Design, synthesis, characterization, and catalytic activity of six enantiomerically pure Ru-based metathesis catalysts are disclosed (3a-3f). The new chiral catalysts were prepared through steric and electronic alterations of the parent catalyst system (3). The present studies indicate that the effect of structural modifications of chiral complex 3 does not always correspond to those of the related achiral complexes. The present findings illustrate that modified Ru complexes (3e and 3f) deliver reactivity levels that are more than 2 orders of magnitude higher than 3. Reactivity and physical data are provided that shed light on the origin of activity differences. Some members of the new generation of chiral Ru catalysts promote asymmetric ring-opening (AROM) and ring-closing (ARCM) metatheses that cannot be effected by the first generation chiral catalyst (3).