Preparation of enediyne-crosslinked networks and their reactivity under thermal and mechanical conditions

The COGEF technique (COnstrained Geometries simulating External Force) was used to investigate the effects of macroscopic forces on cyclic enediynes, which can undergo Bergman Cyclization (BC). Because the forces needed to activate BC were found to be less than the forces needed for chain scission in polymer backbones, the calculations suggest that enediynes are potentially useful mechanophores. Three enediynes studied computationally were synthesized. The thermal BC reactions for these compounds were studied by DSC and found to be consistent with the predicted thermal sensitivity based on known substituent effects. However, upon incorporation of the enediynes into a polymer matrix as crosslinks, no definitive mechanical activation was observed, and conclusions about the stress-sensitivity of enediynes were unable to be drawn. Model studies suggest that insufficient force was applied to the crosslinks for mechanical activation to be observable by DSC.     

On the estimation of interleaved pulse train phases

Some signals are transmitted as periodic pulse trains where information is in the timing of the arrival of the pulses. A number of pulse trains arriving over the same time interval are said to be interleaved. We propose an on-line method for estimating pulse train phases and fine-tuning pulse repetition frequency (PRF) estimates of a known number of interleaved pulse trains. The computational effort is of order N, where N is the number of pulses received. In particular, we employ an extended Kalman filter, where discontinuities in the signal model are appropriately smoothed.     

Factors affecting thresholds for sinusoidal signals in narrow-band maskers with fluctuating envelopes

When a signal is higher in frequency than a narrow-band masker, thresholds are lower when the masker envelope fluctuates than when it is constant. This article investigates the cues used to achieve the lower thresholds, and the factors that influence the amount of threshold reduction. In experiment I the masker was either a sinusoid (constant envelope) or a pair of equal-amplitude sinusoids (fluctuating envelope) centered at the same frequency as the single sinusoid (250, 1000, 3000, or 5275 Hz). The signal frequency was 1.8 times the masker frequency. At all center frequencies, thresholds were lower for the two-tone masker than for the sinusoidal masker, but the effect was smaller at the highest and lowest frequencies. The reduced effect at high frequencies is attributed to the loss of a cue related to phase locking in the auditory nerve. The reduced effect at low frequencies can be partly explained by reduced slopes of the growth-of-masking functions. In experiment II the masker was a sinusoid amplitude modulated at an 8-Hz rate. Masker and signal frequencies were the same as for the first experiment. Randomizing the modulation depth between the two halves of a forced-choice trial had no effect on thresholds, indicating that changes in modulation depth are not used as a cue for signal detection. Thresholds in the modulated masker were higher than would be predicted if they were determined only by the masker level at minima in the envelope, and the threshold reduction produced by modulating the master envelope was less at 250 Hz than at higher frequencies. Experiments III and IV reveal two factors that contribute to the reduced release from masking at low frequencies: The rate of increase of masked threshold with decreasing duration is greater at 250 Hz than at 1000 Hz; the amount of forward masking, relative to simultaneous masking, is greater at 250 Hz than at 1000 Hz. The results are discussed in terms of the relative importance of across-channel cues and within-channel cues.     

Characterization of a 90° microstrip bend with arbitrary mitervia the time-domain finite difference method

A 90° microstrip bend with an arbitrary miter is characterized using the finite difference time-domain (FDTD) method. In this method, to simplify computations, the microstrip structure is enclosed by four electric walls; thus radiation effects are neglected. Time histories generated by FDTD techniques are Fourier-transformed to yield broadband scattering parameters of the microstrip bend. A miter is introduced to improve the transmission characteristics of the bend, and an optimal miter length is found such that the reflection from the microstrip bend over a broad frequency range is minimized     

Evaluation of a Gelatin-Modified Poly(ε-Caprolactone) Film as a Scaffold for Lung Disease

Lung transplantation is a necessary step for the patients with the end stage of chronic obstructive pulmonary disease. The use of artificial lungs is a promising alternative to natural lung transplantation which is complicated and is restricted by low organ donations. For successful lung engineering, it is important to choose the correct combination of specific biological cells and a synthetic carrier polymer. The focus of this study was to investigate the interactions of human lung epithelial cell line NCl-H292 that is involved in lung tissue development with the biodegradable poly(ε-caprolactone) before and after its chemical modification to evaluate potential for use in artificial lung formation. Also, the effect of polymer chemical modification on its mechanical and surface properties has been investigated. The poly(ε-caprolactone) surface was modified using aminolysis followed by immobilization of gelatin. The unmodified and modified polymer surfaces were characterized for roughness, tensile strength, and NCl-H292 metabolic cell activity. The results showed for the first time the possibility for NCI-H292 cells to adhere on this polymeric material. The resazurin assay showed that the metabolic activity at 24?h postseeding of 80% in the presence of the unmodified and greater than 100% in the presence of the modified polymer was observed. The roughness of the poly(ε-caprolactone) increased from 4 to 26?nm and the film strength increased from 0.01 to 0.045 kN when the material was chemically modified. The results obtained to date show potential for using modified poly(ε-caprolactone) as a scaffold for lung tissue engineering.     

Phase-stepped ESPI and moiré interferometry for measuring stress-intensity factor andJ integral

Electronic-speckle-pattern interferometry and moiré interferometry have been used to calculateK ₁ andJ for compact tension specimens. Automated-fringe-pattern analysis enables the full-field of data to be used with the minimum of operator intervention. Measurements are shown to be accurate to within 10 percent. TheJ-measurement procedure employed could form the basis of an automatic-fault detection system.     

Efficient preparation of 2,4-methanoproline

Using a modification of the route described by Clardy and Hughes et al., 2,4-methanoproline hydrochloride (1) was prepared in four steps and 70% overall yield from dl-serine methyl ester.     

Catalytic mechanism of Golgi-resident human tyrosylprotein sulfotransferase-2: A mass spectrometry approach

Human tyrosylprotein sulfotransferases catalyze the transfer of a sulfuryl moiety from the universal sulfate donor PAPS to the hydroxyl substituent of tyrosine residues in proteins and peptides to yield tyrosine sulfated products and PAP. Tyrosine sulfation occurs in the trans-Golgi network, affecting an estimated 1% of the tyrosine residues in all secreted and membrane-bound proteins in higher order eukaryotes. In this study, an effective LC-MS-based TPST kinetics assay was developed and utilized to measure the kinetic properties of human TPST-2 and investigate its catalytic mechanism when G protein-coupled CC-chemokine receptor 8 (CCR8) peptides were used as acceptor substrates. Through initial rate kinetics, product inhibition studies, and radioactive-labeling experiments, our data strongly suggest a two-site ping-pong model for TPST-2 action. In this mechanistic model, the enzyme allows independent binding of substrates to two distinct sites, and involves the formation of a sulfated enzyme covalent intermediate. Some insights on the important amino acid residues at the catalytic site of TPST-2 and its covalent intermediate are also presented. To our knowledge, this is the first detailed study of the reaction kinetics and mechanism reported for human TPST-2 or any other Golgi-resident sulfotransferase.