Kinetics and mechanisms of S(IV) reductions of bromite and chlorite ions

The reaction of bromite with aqueous S(IV) is first order in both reactants and is general-acid catalyzed. The reaction half-lives vary from 5 ms (p[H+] 5.9) to 210 s (p[H+] 13.1) for 0.7 mM excess S(IV) at 25 degrees C. The proposed mechanism includes a rapid reaction (k(1) = 3.0 x 10(7) M(-1) s(-1)) between BrO(2)(-) and SO(3)(2-) to form a steady-state intermediate, (O(2)BrSO(3))(3-). General acids assist the removal of an oxide ion from (O(2)BrSO(3))(3-) to form OBrSO(3)(-), which hydrolyzes rapidly to give OBr(-) and SO(4)(2-). Subsequent fast reactions between HOBr/OBr(-) and SO(3)(2-) give Br(-) and SO(4)(2-) as final products. In contrast, the chlorite reactions with S(IV) are 5-6 orders of magnitude slower. These reactions are specific-acid, not general-acid, catalyzed. In the proposed mechanism, ClO(2)(-) and SO(3)H(-)/SO(2) react to form (OClOSO(3)H)(2)(-) and (OClOSO(2))(-) intermediates which decompose to form OCl(-) and SO(4)(2-). Subsequent fast reactions between HOCl/OCl(-) and S(IV) give Cl- and SO(4)(2-) as final products. SO(2) is 6 orders of magnitude more reactive than SO(3)H-, where k(5)(SO(2)/ClO(2)(-)) = 6.26 x 10(6) M(-1) s(-1) and k(6)(SO(3)H(-)/ClO(2)(-)) = 5.5 M(-1) s(-1). Direct reaction between ClO(2)(-) and SO(3)(2-) is not observed. The presence or absence of general-acid catalysis leads to the proposal of different connectivities for the initial reactive intermediates, where a Br-S bond forms with BrO(2)(-) and SO(3)(2-), while an O-S bond forms with ClO(2)(-) and SO(3)H-.     

Acoustic attenuation of hybrid silencers

The acoustic attenuation of a single-pass, perforated concentric silencer filled with continuous strand fibers is investigated first theoretically and experimentally. The study is then extended to a specific type of hybrid silencer that consists of two single-pass perforated filling chambers combined with a Helmholtz resonator. One-dimensional analytical and three-dimensional boundary element methods (BEM) are employed for the predictions of the acoustic attenuation in the absence of mean flow. To account for the wave propagation in absorbing fiber, the complex-valued characteristic impedance and wave number are measured. The perforation impedance facing the fiber is also presented in terms of complex-valued characteristic impedance and wave number. The effects of outer chamber diameter and the fiber density are examined. Comparisons of predictions with the experiments illustrate the need for multi-dimensional analysis at higher frequencies, while the one-dimensional treatment provides a reasonable accuracy at lower frequencies, as expected. The study also shows a significant improvement in the acoustic attenuation of the silencer due to fiber absorption. Multi-dimensional BEM predictions of a hybrid silencer demonstrate that a reactive component such as a Helmholtz resonator can improve transmission loss at low frequencies and a higher duct porosity may be effective at higher frequencies.     

Der Bestimmung von phosphoriger S?ure, Unterphosphors?ure (H2PO3) und unterphosphoriger S?ure (H3PO2) nebeneinander und neben Phosphors?ure

Ohne Zusammenfassung     

Veränderungen des dielektrischen Relaxationsspektrums von Hochpolymeren durch Verstreckung

Ohne Zusammenfassung Auszug aus der Dissertation von K. Huff, Philipps-Universit?t, Philosophische Fakult?t (Marburg/L. 1956). Ebenso danken wir auch hier nochmals den Firmen Farbenfabriken Bayer, Leverkusen, Badische Anilin & Sodafabriken, Lud-wigshafen, Norddeutsches See-Kabel-werk, Nordenham, Fa. Kalle & Co., Wies-baden-Biebrich und Organico, Paris/für die freundliche überlassung des geeigneten Untersuchungsmaterials.     

Controlling the cellular uptake of gold nanorods

Gold nanorods coated with cetyltrimethylammonium bromide (CTAB), a cationic micellar surfactant used in nanorod synthesis, were rapidly and irreversibly internalized by KB cells via a nonspecific uptake mechanism. Internalized nanorods near the cell surface were monitored by two-photon luminescence (TPL) microscopy and observed to migrate toward the nucleus with a quadratic rate of diffusion. The internalized nanorods were not excreted but formed permanent aggregates within the cells, which remained healthy and grew to confluence over a 5-day period. Nonspecific nanorod uptake could be greatly reduced by displacing the CTAB surfactant layer with chemisorptive surfactants, particularly by the conjugation of poly(ethylene glycol) chains onto nanorods using in situ dithiocarbamate formation.     

On the effects of dephasing due to local gradients in diffusion tensor imaging experiments: relevance for diffusion tensor imaging fiber phantoms

The effect of susceptibility differences between fluid and fibers on the properties of DTI fiber phantoms was investigated. Thereto, machine-made, easily producible and inexpensive DTI fiber phantoms were constructed by winding polyamide fibers of 15 microm diameter around a circular acrylic glass spindle. The achieved fractional anisotropy was 0.78+/-0.02. It is shown by phantom measurements and Monte Carlo simulations that the transversal relaxation time T(2) strongly depends on the angle between the fibers and the B(0) field if the susceptibilities of the fibers and fluid are not identical. In the phantoms, the measured T(2) time at 3 T decreased by 60% for fibers running perpendicular to B(0). Monte Carlo simulations confirmed this result and revealed that the exact relaxation time depends strongly on the exact packing of the fibers. In the phantoms, the measured diffusion was independent of fiber orientation. Monte Carlo simulations revealed that the measured diffusion strongly depends on the exact fiber packing and that field strength and -orientation dependencies of measured diffusion may be minimal for hexagonal packing while the diffusion can be underestimated by more than 50% for cubic packing at 3 T. To overcome these effects, the susceptibilities of fibers and fluid were matched using an aqueous sodium chloride solution (83 g NaCl per kilogram of water). This enables an orientation independent and reliable use of DTI phantoms for evaluation purposes.     

Synthesis of conformationally constrained 5,6,7, 8-Tetrahydroimidazo[1,5-a]pyridine inhibitors of farnesyltransferase

[reaction: see text] Synthesis of the 8-amino-5,6,7,8-tetrahydroimidazo[1,5-a]pyridine ring system was accomplished by intramolecular cyclization of an iminium ion, derived from condensation of an amine and a substituted gamma-(1-imidazolyl)butyraldehyde. The reaction was used to produce conformationally restricted farnesyltransferase inhibitor analogues which exhibit improved in vivo metabolic stability.