Electrochemical determination of triple helices: electrocatalytic oxidation of guanine in an intramolecular triplex

Electrocatalytic oxidation of the oligonucleotide 5'- GAA GAG GTT TTT CCT CTT CTT TTT CTT CTC C (TS) by Ru(bpy)(3)(2+) was studied by cyclic voltammetry. This oligonucleotide forms either an intramolecular triplex, hairpin, or single strand, depending on the pH (Plum, G. E.; Breslauer, K. J. J. Mol. Biol. 1995, 248, 679-695). In the triplex form, the guanine doublet in TS is buried inside the folded structure, and as such is less susceptible to oxidation by electrogenerated Ru(bpy)(3)(3+). Digital simulations of the catalytic voltammograms gave a rate constant of 3.5 +/- 0.2 x 10(2) M(-1) s(-1) for oxidation of the triplex form, while oxidation of the duplex and single-stranded forms occurred with much faster rate constants of (3.5-9.1) x 10(4) M(-1) s(-1). Experiments using a truncated form of TS that lacked the third strand of the triplex were consistent with these measurements. The Ru(bpy)(3)(3+) complex was also generated by photolyzing Ru(bpy)(3)(2+) in the presence of Fe(CN)(6)(3-). This reaction produced strand scission following piperidine treatment, which was visualized using high-resolution gel electrophoresis. These experiments showed decreased reactivity for the triplex form, and also gave an unusual reversal of a common selectivity for the 5'-G of GG doublets generally seen in B-form DNA. This reversal was ascribed to strain caused by the location of the GG doublet adjacent to the hairpin loop.     

Ameisens?ure

Ohne Zusammenfassung     

Efficacy of a Behaviorally Based Voice Therapy Protocol for Vocal Nodules

The aim of this study was to assess the effects on vocal function of voice therapy for vocal nodules. Perceptual and physiological progressive changes were examined during a strictly structured, behaviorally based voice therapy protocol in which 11 women with vocal nodules participated. Randomized audio recordings from pretherapy and from each of the therapy approaches (vocal hygiene, respiration, direct facilitation, carryover) were used for perceptual evaluations. Six speech-language pathologists rated ten voice quality parameters. Two evaluation procedures were performed and compared. Interlistener reliability was sufficiently high in both tests. Significant effects of therapy were found for decreased overall dysphonia, press, instability, gratings, roughness, vocal fry, and "scrape." Nonsignificant group effects were found for breathiness, aphonic instances, and lack of sonority. No significant parameter changes occurred between baseline assessment and the completion of the initial (vocal hygiene) phase of therapy. Significant changes were found following the direct facilitation and respiration phases of therapy. Videostroboscopic evaluations made by two laryngologists showed that in no case were the nodules completely resolved. However, the nodules had decreased in size and edema was reduced after therapy for all clients, but one. Combined results suggest: (1) Alterations in vocal function were reflected in perceptual parameters, and (2) the voice therapy had a positive effect on voice quality, vocal status, and vocal function for the majority of the vocal nodule clients.     

Vibronic coupling in the ground and excited states of the naphthalene cation

The hole-vibrational coupling in naphthalene is studied using high-resolution gas-phase photoelectron spectroscopy and density functional theory calculations (DFT), and a remarkable increase of the coupling with low-frequency vibrations is observed in the excited states.     

The Deletion Method For Upper Tail Estimates

We present a new method to show concentration of the upper tail of random variables that can be written as sums of variables with plenty of independence. We compare our method with the martingale method by Kim and Vu, which often leads to similar results.Some applications are given to the number X _G of copies of a graph G in the random graph (n,p). In particular, for G = K ₄ and G = C ₄ we improve the earlier known upper bounds on —ln (X _G 2 X _G ) in some range of p = p(n).* Research of the second author supported by KBN grants 2 P03A 032 16 and 2 P03A 015 23.     

Flocculation behavior of asphaltenes in solvent/nonsolvent systems

Diffusion coefficients of asphaltenes dissolved in two aromatic solvents, toluene-d(8) or ethylbenzene-d(10), were measured with the pulsed-field gradient spin echo nuclear magnetic resonance (PFG-SE NMR) technique upon addition of flocculant (pentane-d(12) or heptane-d(16)). It was observed that the change in the diffusion coefficients, as a function of amount of added flocculant, was small in the concentration interval studied (up to 30 wt% alkane). Complementary kinetic flocculation studies were made at alkane additions above 55 wt%. The initial change in turbidity upon the addition of alkane was measured with an UV-VIS spectrophotometer. The obtained stability ratio, W, showed that asphaltenes were least stable in the ethylbenzene-pentane system and most stable in the toluene-heptane system. These findings were in agreement with the PFG-SE NMR. When combining the results from the two different techniques it appeared as if there was a dramatic increase in flocculation above a certain "threshold concentration" of added alkane. Furthermore, the flocculation appeared to be reaction controlled until as much as 63 wt% of n-pentane or, alternatively, 68 wt% of n-heptane had been added to the systems, after which the flocculation became primarily diffusion controlled. Finally, careful relaxation measurements showed that the asphaltenes displayed two distinctly different transverse (T(2)) relaxation times (most probably averages), one at 0.6 ms and the other at 7 ms.