Wind-generated ambient noise in a topographically isolated basin: a pre-industrial era proxy

During the mid-1980s, calibrated measurements of ambient noise and wind speed were made in the Tongue of the Ocean in the Bahamas to quantify the spectra and statistics of wind-generated noise. This deep basin is topographically isolated from the Atlantic Ocean and, therefore, largely acoustically decoupled from the Atlantic Ocean deep sound channel. The quantitative effects of contaminating (non-surface wind-generated) noise sources within the basin were eliminated by careful measurement and robust statistical analysis methodologies. Above 500 Hz, the spectral slopes are approximately -5 dB per octave and independent of wind speed. Below 500 Hz, the ambient noise is no longer a linear function of wind speed. Below 100 Hz and for wind speeds greater than 18.5 knots (kt), the ambient noise is independent of frequency. The minimum observed ambient noise level falls 13 dB below Urick's "light shipping" level at 30 Hz and 2-5 dB below Wenz's sea state zero level through the wind-dominated portion of the spectrum. The basin's geographical isolation and the rigorous measurement and analysis methodologies employed make this two-decade-old data set a reasonable and justified proxy for pre-industrial era ocean noise levels in the 20 Hz to 20 kHz frequency band.     

FDA Quality assurance for radioactivity in foods and radiopharmaceuticals

Summary The Food and Drug Administration (FDA) has regulatory responsibility for radionuclides in foods and radiopharmaceuticals and must maintain an ongoing Quality Assurance Program. These Quality Control Programs involve the U.S. Environmental Protection Agency (EPA) [1, 2] and the National Institute of Standards and Technology (NIST) [3], who supply the necessary reference materials and standards to ensure that the measurements are accurate and reproduceable. Data from EPA (1987 to 1991) and from a NIST Blind Source study (1985 to 1991) show the results are accurate with an average variation from NIST values of 1.8% [4–10]. The use of standard materials with the same matrices as the samples being analyzed provides credibility to the measurements.     

Excited-state electron-transfer quenching by a series of water photoreduction mediators

Rate constants k_q for the quenching of the excited state of Ru(bipy)₃²⁺ by a series of viologen salts having different redox potential E_{$\text{1}\text{2}$} have been determined in deaerated aqueous solutions at pH = 5 by laser flash photolysis. The k_q values are found to decrease with increasing —E_{$\text{1}\text{2}$} and to correlate with the reaction free-energy change ΔG. Such a correlation is shown to be consistent with the Rehm—Weller model for electron-transfer reactions.     

Synthesis and reactivity of pelletierine-derived building blocks and pelletierine analogs

Lycopodium alkaloids are unique (and often impressive in terms of structures) polycyclic alkaloids that attract great interest from a biological point of view and that also provide ideal targets for total synthesis. Propylpiperidine units closely related to pelletierine are involved in the biosynthesis of these alkaloids. Therefore, stable pelletierine-like compounds, especially a (R)-phenylglycinol-based oxazolopiperidine analog, were prepared and their reactivity investigated. The compounds described in this work expand the tool-box of small building blocks in the piperidine series and pelletierine analogs and could be suitable for the synthesis of Lycopodium alkaloids following biosynthetically inspired strategies.     

Facile, aprotic degradation of η-CpZrCl3·dme by ternary sodium/group 14 tert-butoxides: From η-CpZrCl3·dme back to NaCp in two easy steps

CpZrCl₃·dme was treated with Na[El(O^tBu)₃], El = Ge, Sn, Pb, respectively. The addition of Na[Sn(O^tBu)₃] to CpZrCl₃·dme caused rapid cyclopentadienide loss and the equally rapid appearance of CpSnCl, half of which crystallized as the trinuclear complex {[ZrCl(O^tBu)₃]₂·CpSnCl}. Pristine CpSnCl reacted almost instantly with NaO^tBu to give NaCp and Na[Sn(O^tBu)₃], which co-crystallized as a coordination polymer. Na[Ge(O^tBu)₃] also displaced Cp from zirconium, but with a different product distribution, giving Cp₂Ge, fac-[Ge(μ-^tBuO)₃ZrCl(O^tBu)₂], and ZrCl(O^tBu)₃. By contrast, Na[Pb(O^tBu)₃] only exchanged its tert-butoxide groups with zirconium to furnish CpZr(O^tBu)₃ and PbCl₂. The solid-state structures of {[ZrCl(O^tBu)₃]₂·CpSnCl}, fac-[Ge(μ-^tBuO)₃ZrCl(O^tBu)₂], and {NaCp·Na[Sn(O^tBu)₃]}_n were determined.     

Franck-Condon simulation, including anharmonicity, of the photodetachment spectrum of P2H(-): restricted-spin coupled-cluster single-double plus perturbative triple and unrestricted-spin coupled-cluster single-double plus perturbative triple -F12x potential energy functions of P2H and P2H(-)

Geometry optimization and harmonic vibrational frequency calculations have been carried out on the X?(2)A(') state of P(2)H and the X?(1)A(') state of P(2)H(-) using the restricted-spin coupled-cluster single-double plus perturbative triple excitation [RCCSD(T)] and explicitly correlated unrestricted-spin coupled-cluster single-double plus perturbative triple excitation [UCCSD(T)-F12x] methods. For RCCSD(T) calculations, basis sets of up to the augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality were employed, and contributions from extrapolation to the complete basis set limit and from core correlation of the P 2s(2)2p(6) electrons were also included. For UCCSD(T)-F12x calculations, different atomic orbital basis sets of triple-zeta quality with different associated complementary auxiliary basis sets and different geminal Slater exponents were used. When the P 2s(2)2p(6) core electrons were correlated in these F12x calculations, appropriate core-valence basis sets were employed. In addition, potential energy functions (PEFs) of the X?(2)A(') state of P(2)H and the X?(1)A(') state of P(2)H(-) were computed at different RCCSD(T) and UCCSD(T)-F12x levels, and were used in variational calculations of anharmonic vibrational wavefunctions, which were then utilized to calculate Franck-Condon factors (FCFs) between these two states, employing a method which includes allowance for anharmonicity and Duschinsky rotation. The photodetachment spectrum of P(2)H(-) was then simulated using the computed FCFs. Simulated spectra obtained using the RCCSD(T)/aug-cc-pV5Z and UCCSD(T)-F12x(x = a or b)/aug-cc-pCVTZ PEFs are compared and found to be essentially identical. Based on the computed FCFs, a more detailed assignment of the observed vibrational structure than previously reported, which includes "hot bands," has been proposed. Comparison between simulated and available experimental spectra has been made, and the currently most reliable sets of equilibrium geometrical parameters for P(2)H and its anion have been derived. The photodetachment spectrum of P(2)D, yet to be recorded, has also been simulated.     

Expression and Characterization of the Intracellular Part of Receptor Protein Tyrosine Phosphatase PTPRU

PTPRU is an MAM domain-containing receptor-like protein tyrosine phosphatase. Previous studies have demonstrated an important role of the enzyme in the maintenance of epithelial integrity and in the regulation of the Wnt/β-catenin signaling pathway. To better understand the function of PTPRU, we cloned and expressed the intracellular portion of PTPRU as a GST fusion protein in E. coli cells. We purified the protein to homogeneity and used it to immunize mice for antibody production. The resultant antibody s...     

Detailed analysis of α,ω-bis(4-hydroxybutyl) poly(dimethylsiloxane) using GPC-MALDI TOF mass spectrometry

In this study the prepolymer alpha,omega-bis(4-hydroxybutyl) poly(dimethylsiloxane), used in the formulation of oxygen permeable films, is evaluated by gel permeation chromatography (GPC) combined with matrix assisted laser desorption ionization (MALDI) time of flight (TOF) mass spectrometry (MS). Two unexpected mass distributions are observed in the mass spectra. Reaction schemes for the formation of these distributions are proposed. A solution phase trimethylsilane end group modification was performed on the prepolymer to determine whether the unexpected mass distributions occur as impurities from synthesis or as artifacts from the MS process. Evaluation of the TMS modified prepolymer indicates the unexpected mass distributions indeed occur as impurities from the synthetic procedure. Average molecular weight values are determined by traditional GPC, direct MALDI-TOF MS, and GPC-MALDI-TOF MS methods and the results are compared.