Possibilities and pitfalls in quantifying the extent of cysteine sulfenic acid modification of specific proteins within complex biofluids

Background  

Cysteine sulfenic acid (Cys-SOH) plays important roles in the redox regulation of numerous proteins. As a relatively unstable posttranslational protein modification it is difficult to quantify the degree to which any particular protein is modified by Cys-SOH within a complex biological environment. The goal of these studies was to move a step beyond detection and into the relative quantification of Cys-SOH within specific proteins found in a complex biological setting--namely, human plasma.     

Benzenoid links

In this paper, we study new configurations of benzenoid hydrocarbons, called benzenoid links. Roughly speaking, a primitive corofusene is a closed narrow hexagonal ribbon with out-of-plane curvature 0. A primitive corofusene or the union of disjoint primitive corofusenes in \mathbbR³{\mathbb{R}^{3}} is called a benzenoid link. In this paper, we determine the minimum number of hexagons needed for a nontrivial benzenoid link in different senses. We also determine the structures of the smallest and the second smallest nontrivial benzenoid links of different types and their numbers of Kekule structures. We list all the benzenoid Hopf links of type III with 22–25 hexagons by their canonical codes in the appendix.     

Green's function for a third-order generalized right focal problem

We determine the Green's function for the third-order three-point generalized right focal boundary value problem

     

Simulation of ultrasonic focus aberration and correction through human tissue

Ultrasonic focusing in two dimensions has been investigated by calculating the propagation of ultrasonic pulses through cross-sectional models of human abdominal wall and breast. Propagation calculations used a full-wave k-space method that accounts for spatial variations in density, sound speed, and frequency-dependent absorption and includes perfectly matched layer absorbing boundary conditions. To obtain a distorted receive wavefront, propagation from a point source through the tissue path was computed. Receive focusing used an angular spectrum method. Transmit focusing was accomplished by propagating a pressure wavefront from a virtual array through the tissue path. As well as uncompensated focusing, focusing that employed time-shift compensation and time-shift compensation after backpropagation was investigated in both transmit and receive and time reversal was investigated for transmit focusing in addition. The results indicate, consistent with measurements, that breast causes greater focus degradation than abdominal wall. The investigated compensation methods corrected the receive focus better than the transmit focus. Time-shift compensation after backpropagation improved the focus from that obtained using time-shift compensation alone but the improvement was less in transmit focusing than in receive focusing. Transmit focusing by time reversal resulted in lower sidelobes but larger mainlobes than the other investigated transmit focus compensation methods.     

Ear-canal acoustic admittance and reflectance measurements in human neonates. II. Predictions of middle-ear in dysfunction and sensorineural hearing loss

This report describes relationships between middle-ear measurements of acoustic admittance and energy reflectance (YR) and measurements of hearing status using visual reinforcement audiometry in a neonatal hearing-screening population. Analyses were performed on 2638 ears in which combined measurements were obtained [Norton et al., Ear Hear. 21, 348-356 (2000)]. The measurements included distortion-product otoacoustic emissions (DPOAE), transient evoked otoacoustic emissions (TEOAE), and auditory brainstem responses (ABR). Models to predict hearing status using DPOAEs, TEOAEs, or ABRs were each improved by the addition of the YR factors as interactions, in which factors were calculated using factor loadings from Keefe et al. [J. Acoust. Soc. Am. 113, 389-406 (2003)]. This result suggests that information on middle-ear status improves the ability to predict hearing status. The YR factors were used to construct a middle-ear dysfunction test on 1027 normal-hearing ears in which DPOAE and TEOAE responses were either both present or both absent, the latter condition being viewed as indicative of middle-ear dysfunction. The middle-ear dysfunction test classified these ears with a nonparametric area (A) under the relative operating characteristic curve of A = 0.86, and classified normal-hearing ears that failed two-stage hearing-screening tests with areas A = 0.84 for DPOAE/ABR, and A = 0.81 for TEOAE/ABR tests. The middle-ear dysfunction test adequately generalized to a new sample population (A = 0.82).     

Effects of fundamental frequency and vocal-tract length changes on attention to one of two simultaneous talkers

Three experiments used the Coordinated Response Measure task to examine the roles that differences in F0 and differences in vocal-tract length have on the ability to attend to one of two simultaneous speech signals. The first experiment asked how increases in the natural F0 difference between two sentences (originally spoken by the same talker) affected listeners' ability to attend to one of the sentences. The second experiment used differences in vocal-tract length, and the third used both F0 and vocal-tract length differences. Differences in F0 greater than 2 semitones produced systematic improvements in performance. Differences in vocal-tract length produced systematic improvements in performance when the ratio of lengths was 1.08 or greater, particularly when the shorter vocal tract belonged to the target talker. Neither of these manipulations produced improvements in performance as great as those produced by a different-sex talker. Systematic changes in both F0 and vocal-tract length that simulated an incremental shift in gender produced substantially larger improvements in performance than did differences in F0 or vocal-tract length alone. In general, shifting one of two utterances spoken by a female voice towards a male voice produces a greater improvement in performance than shifting male towards female. The increase in performance varied with the intonation patterns of individual talkers, being smallest for those talkers who showed most variability in their intonation patterns between different utterances.     

Blind estimation of reverberation time

The reverberation time (RT) is an important parameter for characterizing the quality of an auditory space. Sounds in reverberant environments are subject to coloration. This affects speech intelligibility and sound localization. Many state-of-the-art audio signal processing algorithms, for example in hearing-aids and telephony, are expected to have the ability to characterize the listening environment, and turn on an appropriate processing strategy accordingly. Thus, a method for characterization of room RT based on passively received microphone signals represents an important enabling technology. Current RT estimators, such as Schroeder's method, depend on a controlled sound source, and thus cannot produce an online, blind RT estimate. Here, a method for estimating RT without prior knowledge of sound sources or room geometry is presented. The diffusive tail of reverberation was modeled as an exponentially damped Gaussian white noise process. The time-constant of the decay, which provided a measure of the RT, was estimated using a maximum-likelihood procedure. The estimates were obtained continuously, and an order-statistics filter was used to extract the most likely RT from the accumulated estimates. The procedure was illustrated for connected speech. Results obtained for simulated and real room data are in good agreement with the real RT values.     

Anion receptors: a new class of amide/quaternized amine macrocycles and the chelate effect

A new class of tetraamide macrocyclic receptors for anions with two quaternized amine functionalities exhibited higher affinities for anions compared with the corresponding neutral amides. In two crystal structures of halide complexes of the prototypes with phenyl and pyridine spacers, the anions are held by hydrogen bonding with the amide hydrogens. The pyridine analogues display higher affinities in general than the phenyl systems, a phenomenon which is attributed to the anion version of the chelate effect.     

Molecular mass determination of saturated hydrocarbons: reactivity of eta5-cyclopentadienylcobalt ion (CpCo*+) and linear alkanes up to C-30

The present study demonstrates the feasibility of the eta5-cyclopentadienylcobalt ion (CpCo*+) as a suitable cationization reagent for saturated hydrocarbon analysis by mass spectrometry. Ion/molecule reactions of CpCo*+ and three medium chain-length n-alkanes were examined using Fourier-transform ion cyclotron resonance mass spectrometry. Second-order rate constants and reaction efficiencies were determined for the reactions studied. Loss of two hydrogen molecules from the CpCo-alkane ion complex was found to dominate all reactions ( > or = 80%). Furthermore, this dehydrogenation reaction efficiency increases with increasing chain length. These preliminary results suggest that the CpCo*+ ion may be a promising cationization reagent of longer chain saturated hydrocarbons and polyolefins.     

Structural studies of N-2-(6-picolyl)-N′-tolylthioureas

Reaction of 2-amino-6-picoline with 2-, 3-, and 4-tolyl isothiocyanates produces the three N-2-(6-picolyl)-N-tolylthioureas, 6PicTu2T, 6PicTu3T, and 6PicTu4T. 6PicTu2T is mono-clinic, space group P2₁/n with a = 8.1700(3) Å, b = 25.5840(6) Å, c = 12.6840(5) Å, = 98.8750(16)°, and V = 2619.5(2) ų with Z = 8, for d _calc = 1.305 g/cm³. 6PicTu3T is monoclinic, space group C2/c with a = 23.879(3) Å, b = 6.744(3) Å, c = 17.116(10) Å, = 99.26(4)°, and V = 2720(3) ų with Z = 8, for d _calc = 1.257 g/cm³. 6PicTu4T is triclinic, space group P-1 with a = 8.829(6) Å, b = 8.8950(15) Å, c = 10.495(3) Å, = 68.63(3)°, = 72.19(4)°, = 63.06(4)°, and V = 681.2(5) ų with Z = 2, for d _calc = 1.255 g/cm³. Intermolecular hydrogen bonding involving the thione sulfur and the NH hydrogen and the planarity of the thiourea are affected by the position of substitution on the aryl ring. ¹H NMR studies in CDCl₃ show the NH hydrogen resonance considerably downfield from other signals in the spectrum of each thiourea. The enthalpies of fusion of the present thioureas reflect the extent of intermolecular hydrogen bonding and are compared to other heterocyclic thioureas.