Nonoccupational noise: exposures associated with routine activities

Efforts to characterize nonoccupational noise exposures have focused primarily on infrequent, episodic events. Few studies have assessed noise levels resulting from routine daily activities. In the current study, 112 construction workers wore datalogging noise dosimeters and simultaneously completed activity logs during two phases of data collection. The 81 subjects monitored in phase 1 received logs listing numerous preselected occupational and nonoccupational activities, while the 31 subjects monitored in phase 2 used free-field logs and reported nonoccupational activities in greater detail. Nearly all of the 221,439 1-min intervals of nonoccupational L(eq) level and activity reporting were below 70 dBA; only a small percentage exceeded 80 dBA. The primary contributor to nonoccupational noise exposure was traveling in a car or bus, while time at home contributed the least. One hundred seventy 24-h L(eq) levels were computed from the 1-min noise level data. The percentage of phase 2 workday L(eq(24)) levels which exceeded 80 dBA was higher than that of the nonworkday levels. The mean L(eq(24)) level of phase 2 workdays was higher than that of nonworkdays, and the difference was statistically significant. Routine nonoccupational noise exposures contributed much less to total noise dose than occupational exposures in the subjects evaluated.     

Synthesis of isochrysohermidin-distamycin hybrids

The synthesis of the alkylating subunit of the DNA cross-linking agent, isochrysohermidin (2), and its subsequent incorporation into conjugates with distamycin A (1) are described. The DNA binding properties of these agents were compared to that of distamycin A, using a fluorescence intercalator displacement (FID) assay.     

An investigation of the chemical stability of arsenosugars in basic environments using IC-ICP-MS and IC-ESI-MS/MS

This paper evaluates the chemical stability of four arsenosugars using tetramethylammonium hydroxide (TMAOH) as an extraction solvent. This solvent was chosen because of the near quantitative removal of these arsenicals from difficult to extract seafood (oysters and shellfish). Four arsenosugars (3-[5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropylene glycol--As(328), 3-5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropanesulfonic acid--As(392), 3-[5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropyl hydrogen sulfate--As(408), and 3-[5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropyl-2,3-hydroxypropyl phosphate--As(482)) were evaluated. The stability of these four arsenosugars were studied independently in a solution of 2.5% TMAOH at 60 degrees C over a period of up to 8 h. Two arsenosugars, As(328) and As(392), were found to be relatively stable in this solution for up to 8 h. However, As(408) and As(482) formed detectable quantities of dimethylarsinic acid (DMAA) and As(328) within 0.5 and 2 h, respectively. It was found that 97% of As(408) degrades after 8 h of treatment producing 3.4 times as much DMAA as As(328). This is contrary to As(482), which produces 13 times as much As(328) as DMAA and only 37% of the As(482) was converted by the 8 h treatment at 60 degrees C. These degradation products led to the investigation of weaker TMAOH extraction solvents. Three different concentrations (2.5%, 0.83% and 0.25%) were used to determine the effect of TMAOH concentration on the degradation rate of As(408). By reducing the TMAOH concentration to 0.83%, the conversion of the arsenosugar to As(328) and DMAA is nearly eliminated (less than 5% loss). Arsenosugars, As(408) and As(482), were also studied in 253 mM NaOH to verify the degradation products. The NaOH experiments were conducted to investigate a possible hydroxide based reaction mechanism. Similar degradation plots were found for each arsenosugar when compared to the 2.5% TMAOH data. A mechanism has been proposed for the formation of As(328) from As(408) and As(482) in base via an SN2 reaction (hydroxide attack) at the side chain carbon adjacent to the inorganic ester. The formation of DMAA is observed in all arsenosugars after prolonged exposure. This probably occurs via an SN2 attack at the arsenic atom.     

Synthesis of biologically active dicarba analogues of the peptide hormone oxytocin using ring-closing metathesis

Facile synthesis of cis and trans olefinic analogues of oxytocin 1 that have carbon in place of sulfur is achieved via ring-closing metathesis (RCM) on a resin-bound linear precursor peptide. Hydrogenation of the cis olefin, 3, proceeds selectively to generate the previously reported saturated derivative 5. Biological testing on rat uterus strips shows that cis compound 3 has an EC50 value of 38 ng/mL (EC50 for oxytocin is 2.7 ng/mL) whereas 5 and trans olefin 4 are less active. [reaction--see text]     

Treatment of radioactive wastes: an X-ray absorption spectroscopy study of the reaction of technetium with green rust

Technetium is a long-lived product of nuclear fission that readily forms the soluble pertechnetate anion [TcO(4)](-). Green rusts (layered hydrous oxides containing both Fe(II) and Fe(III) and with interlayer sulfate or carbonate anions) concentrate >99.8% of 99Tc, present as [TcO(4)](-), from aqueous solution, even in the presence of high concentrations of NaNO(3), a common constituent of radioactive waste streams. The mechanism of removal from solution is apparently reduction and formation of strong Tc(IV) surface complexes. X-ray absorption spectroscopy shows that [TcO(4)](-) is indeed reduced by reaction with both sulfate- and carbonate-form green rusts and is found in a TcO(2)-like environment. On contact with air, the green rusts oxidize to poorly crystalline goethite but the Tc environment is unchanged. There is no increase in Tc solubility associated with oxidation of the host green rust. This behavior suggests that green rusts may be useful in the treatment of Tc-containing waste streams, in groundwater cleanup, and in restricting Tc migration from repositories.     

Relative contributions of spectral and temporal cues for phoneme recognition

Cochlear implants provide users with limited spectral and temporal information. In this study, the amount of spectral and temporal information was systematically varied through simulations of cochlear implant processors using a noise-excited vocoder. Spectral information was controlled by varying the number of channels between 1 and 16, and temporal information was controlled by varying the lowpass cutoff frequencies of the envelope extractors from 1 to 512 Hz. Consonants and vowels processed using those conditions were presented to seven normal-hearing native-English-speaking listeners for identification. The results demonstrated that both spectral and temporal cues were important for consonant and vowel recognition with the spectral cues having a greater effect than the temporal cues for the ranges of numbers of channels and lowpass cutoff frequencies tested. The lowpass cutoff for asymptotic performance in consonant and vowel recognition was 16 and 4 Hz, respectively. The number of channels at which performance plateaued for consonants and vowels was 8 and 12, respectively. Within the above-mentioned ranges of lowpass cutoff frequency and number of channels, the temporal and spectral cues showed a tradeoff for phoneme recognition. Information transfer analyses showed different relative contributions of spectral and temporal cues in the perception of various phonetic/acoustic features.     

Chromium(0)-promoted multicomponent cycloaddition of tethered diynes with cyclic trienes: application to the total synthesis of 9-epi-pentalenic acid

An efficient protecting group controlled regioselective chromium(0)-mediated three-component higher order cycloaddition of tethered diynes with cyclic trienes that generates five rings and six stereogenic centers in one step is described. Following a sequence of reactions featuring a chemoselective Baeyer-Villiger rearrangement and a regioselective cyclopropane hydrogenolysis, the total synthesis of 9-epi-pentalenic acid was achieved.     

Scanning probe lithography on fluid lipid membranes

Scanning probe lithography (SPL) is applied to pattern fluid lipid membranes on a solid borosilicate substrate. Grids of metal lines, prepatterned onto the substrate by electron beam lithography, serve to partition the supported membrane into an array of isolated fluid pixels. By toggling the pH of the surrounding solution, the effect of the probe tip on the membrane can be regulated. Alkaline conditions favor membrane removal, while neutral pH favors membrane deposition. Arbitrary membrane patterns with spatial dimensions limited by the underlying grid size can be constructed by sequential SPL membrane removal followed by refill with a different membrane type. In the present study, bilayers of unique composition fill 1 x 1 mum corrals and were positioned 100 nm apart.     

Scavenging and reclaiming phosphines associated with group 10 metal-mediated couplings

[reaction: see text] Exposure of any of several mono- or bidentate phosphines to CuCl leads to quick removal of unwanted ligands from solution. Most phosphines, if desired, can be easily recovered.     

Curves of positive solutions of boundary value problems on time-scales

Let TR be a time-scale, with a=infT, b=supT. We consider the nonlinear boundary value problem

(2)

(4)

u(a)=u(b)=0,