1H and 13C NMR spectroscopic study of oxidation of D,L‐cystine and 3,3′‐dithiobis(propionic acid) with hydrogen peroxide in aqueous solution

The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D₂O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu²⁺ cations, but not Fe³⁺ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd.     

Stationary entanglement between macroscopic mechanical oscillators

We show that the optomechanical coupling between an optical cavity mode and two movable cavity mirrors is able to entangle two different macroscopic oscillation modes of the mirrors. This continuous variable entanglement is maintained by the light bouncing between the mirrors and is robust against thermal noise. In fact, it could be experimentally demonstrated using present technology. Received 2 September 2002 / Received in final form 10 October 2002 Published online 7 January 2003     

Rotational analysis ofA 1Π-X 1Σ+ bands of P14N and P15N: Perturbatio studies in theA 1Π state

The ultraviolet band systemsA ¹Π-X ¹Σ⁺ of P¹⁴N and P¹⁵N were excited in an electrodeless tube containing traces of phosphorus specpure nitrogen and neon using a microwave discharge (2450 MHz). Bands of the isotopic species, P¹⁵N, were obtained using¹⁵N₂ enriched to 95.5%. Rotational analyses of eleven bands of P¹⁴N and sixteen bands of P¹⁵N were carried out. Three perturbing statese ³Σ⁻,d ³Δ andb ³Π, arising from the lower valence configurations were identified from the observed perturbations in thev′=0–4 levels of theA ¹Π state. Deperturbation studies led to the determination of molecular constants of the perturbing states. Vibrational assignments of the perturbing states were made from isotope shift studies.     

Structure and Structural Nonrigidity of Tetrachlorodibenzo-p-Dioxin Radical Cations

Ab initio calculations showed that the tetrachlorodibenzo-para-dioxin radical cations (TCDD RCs) with a planar structure have two steady states with asymmetric dioxin cycles. The activation barriers between these states are up to 2 kcal/mole, so that the RCs may be regarded as being structurally nonrigid within the dioxin cycle. The 2,3,7,8-TCDD RC is more stable than the 1,4,6,9-TCDD RC, the energy difference being 5.2 kcal/mole. The adiabatic ionization potential of 2,3,7,8-TCDD (7.54 eV) is 0.1 eV smaller than the corresponding potential of 1,4,6,9-TCDD. These factors account for the increased hemoproteide affinity and hence increased biological activity of 2,3,7,8-TCDD.     

Synthesis and Crystal Structure of the Hydrogen Polyphosphide Bis(Tetraphenylphosphonium) hydrogenheptaphosphide‐ammonia(1/3) (PPh4)2HP7 · 3NH3

(PPh₄)₂HP₇ · 3NH₃ was prepared by the reaction of K₃P₇ with a proton‐charged ion exchange resin in the presence of (PPh₄)Br in liquid ammonia, and characterized by low temperature X‐ray structure analysis. The thermally very unstable compound contains the hydrogenheptaphosphide anion HPequation/tex2gif-stack-1.gif, the nortricyclane‐like cage of which is slightly distorted by the attachment of the hydrogen atom.     

Synthesis and conformational investigation of tetrapeptide analogues of the fragment B23-B26 of insulin

Tetrapeptides containing one of a set of four different α,α-dialkyl glycines at the C-terminus were synthesized by conventional methods in solution and their conformational behavior investigated by ¹H NMR spectroscopy in connection with molecular mechanics calculations. The results were consistent with conformations stabilized by a γ-turn in the case of compounds with alkyl groups larger than methyl, while the corresponding Aib derivative did not exhibit intramolecular hydrogen bonding.     

Numerical simulations of a filament in a flowing soap film

Experiments concerning the properties of soap films have recently been carried out and these systems have been proposed as experimental versions of theoretical two‐dimensional liquids. A silk filament introduced into a flowing soap film, was seen to demonstrate various stable modes, and these were, namely, a mode in which the filament oscillates and one in which the filament is stationary and aligns with the flow of the liquid. The system could be forced from the oscillatory mode into the non‐ oscillatory mode by varying the length of the filament. In this article we use numerical and computational techniques in order to simulate the strongly coupled behaviour of the filament and the fluid. Preliminary results are presented for the specific case in which the filament is seen to oscillate continuously for the duration of our simulation. We also find that the filament oscillations are strongly suppressed when we reduce the effective length of the filament. We believe that these results are reminiscent of the different oscillatory and non‐oscillatory modes observed in experiment. The numerical solutions show that, in contrast to experiment, vortices are created at the leading edge of the filament and are preferentially grown in the curvature of the filament and are eventually released from the trailing edge of the filament. In a similar manner to oscillating hydrofoils, it seems that the oscillating filaments are in a minimal energy state, extracting sufficient energy from the fluid to oscillate. In comparing numerical and experimental results it is possible that the soap film does have an effect on the fluid flow especially in the boundary layer where surface tension forces are large. Copyright © 2004 John Wiley & Sons, Ltd.     

LINEAR ACTIVE STRUCTURES AND MODES (Ⅱ)--DISCRETE SYSTEMS AND BEAMS

The basic concepts about the active structures and some attributes of the modes were presented in paper "Liner Active Structures and Modes ( Ⅰ ) ". The characteristics of the active discrete systems and active beams were discussed, especially, the stability of the active structures and the orthogonality of the eigenvectors. The notes about modes were portrayed by a model of a seven-storeyed building with sensors and actuators. The concept of the adjoint active structure was extended from the discrete systems to the beams that were the representations of the continuous structures. Two types of beams with different placements of the measuring and actuating systems were discussed in detail. One is the beam with the discrete sensors and actuators, and the other is the beam with distributed sensor and actuator function. The orthogonality conditions were derived with the modal shapes of the active beam and its adjoint active beam. An example shows that the variation of eigenvalues with feedback amplitude for the homo-configuration and non-homo-configuration active structures.