Nitrogen inversion in cyclic amines and the bicyclic effect

The hitherto unsolved problem of the origin of the unusually high nitrogen inversion-rotation (NIR) barriers in 7-azabicyclo[2.2.1]heptanes (the bicyclic effect) was examined using the natural bond orbital (NBO) approach. Reinvestigating the NIR barrier for tropane by DNMR, we found that NIR barriers increase smoothly on going from nitrogen-bridged bicyclic systems of a larger ring size to the smaller ring homologous systems. The experimental NIR barriers are reproduced with good accuracy using the MP2/6-31G level of theory. The NBO analysis for these and other azabicycles led to the conclusion that the height of these barriers is mostly determined by the energy of the sigma-orbitals of the C(alpha)(-)C(beta) bonds as well as the nitrogen lone pair. Thus, the bicyclic effect is actually an extreme case of a common C(alpha-)N-C(alpha) tripyramid geometry-NIR barrier dependence for N-bridged bicyclic amines. By establishing the rate-determining role of the C(alpha-)N-C(alpha) tripyramid fragment for NIR, we have derived the first sufficiently accurate quantitative correlations amine geometry-NIR barrier for monocyclic as well as bicyclic N-H and N-Me amines (i.e., for an amine set which also includes the bicyclic effect systems).     

Photodynamics of the bacteriochlorophyll-carotenoid system. 2. Influence of central metal,solvent and beta-carotene on photobleaching of bacteriochlorophyll derivatives

Bacteriochlorophyll (BChl) derivatives (with central Mg replaced by metal "M") ([M]-BChl with M = 2H, Mg, Zn, Pd, Cu) have been investigated for their photodynamic capacity and stability toward photodegradation in organic solvents and aqueous micellar solution. A protocol has been developed for screening new sensitizers. BChl and [Zn]-BChl are efficient sensitizers, but they are also quickly degraded by the reactive oxygen species (ROS) produced by autosensitization, as well as by hetero-sensitization with 17(4)-methyl-13(2)-demethoxycarbonyl-pheophorbide a (MPP). Photostable [Cu]-BChl is a poor sensitizer, whereas [Pd]-BChl and bacteriopheophytin a are not only very efficient sensitizers but are also very stable toward ROS. beta-Carotene is no efficient physical quencher of ROS in the system; rather, it acts as a photochemical quencher that competes with [M]-BChl and undergoes photooxygenation at high rates. Photolability seems to depend on the pigment oxidation potential and, in parallel, on the presence of central metals preferring coordination numbers higher than 4, whereas photodynamic capacity depends on long excited state life-times of the pigment or efficient intersystem crossing (or both).     

Stereochemical study of phosphonothioate cleavage by a metallomicelle

[reaction: see text] The copper metallomicellar hydrolysis of O-methyl O-4-nitrophenyl phenylphosphonothioate to O-methyl phenylphosphonothioic acid takes place with effectively complete inversion at phosphorus.     

A recyclable chiral Ru catalyst for enantioselective olefin metathesis. Efficient catalytic asymmetric ring-opening/cross metathesis in air

The synthesis and structure of a new chiral bidentate imidazolinylidene ligand and a derived chiral Ru-based carbene are disclosed. The Ru complex is stereogenic at the metal center; it can be prepared in >98% diastereoselectivity and purified by silica gel chromatography with undistilled solvents. The air-stable Ru complex efficiently catalyzes ring-closing and ring-opening metathesis and is recyclable. The chiral complex is highly effective (0.5-10 mol % loading) in promoting enantioselective ring-opening/cross metathesis reactions (up to >98% ee). These enantioselective transformations can be effected in air, with unpurified solvent and with substrates that would only polymerize with Mo-based catalysts.     

Quantum cloning with an optical fiber amplifier

It has been shown theoretically that a light amplifier working on the physical principle of stimulated emission should achieve optimal quantum cloning of the polarization state of light. We demonstrate close-to-optimal universal quantum cloning of polarization in a standard fiber amplifier for telecom wavelengths. For cloning 1-->2 we find a fidelity of 0.82, the optimal value being 5 / 6=0.83.     

Two definitions of exponential dichotomy for skew-product semiflow in Banach spaces

In this paper we introduce a concept of exponential dichotomy for linear skew-product semiflows (LSPS) in infinite dimensional Banach spaces, which is an extension of the classical concept of exponential dichotomy for time dependent linear differential equations in Banach spaces. We prove that the concept of exponential dichotomy used by Sacker-Sell and Magalhães in recent years is stronger than this one, but they are equivalent under suitable conditions. Using this concept we where able to find a formula for all the bounded negative continuations. After that, we characterize the stable and unstable subbundles in terms of the boundedness of the corresponding projector along (forward/backward) the LSPS and in terms of the exponential decay of the semiflow. The linear theory presented here provides a foundation for studying the nonlinear theory. Also, this concept can be used to study the existence of exponential dichotomy and the roughness property for LSPS.

     

Kinetische Untersuchungen über die Silicium—Aryl-Spaltung mit Bromwasserstoff

Rate constants of the cleavage reaction of silicon aryl linkages with HBr were estimated for various aryl derivatives by means of NMR. A row of substituents was obtained, dependent on the cleavage rates. Correlation with theHammett function shows the electrophilic character of the reaction. The different cleavage rates give the possibility for specific cleavages of aryl groups from silanes.

     

Localization ability with bimodal hearing aids and bilateral cochlear implants

After successful cochlear implantation in one ear, some patients continue to use a hearing aid at the contralateral ear. They report an improved reception of speech, especially in noise, as well as a better perception of music when the hearing aid and cochlear implant are used in this bimodal combination. Some individuals in this bimodal patient group also report the impression of an improved localization ability. Similar experiences are reported by the group of bilateral cochlear implantees. In this study, a survey of 11 bimodally and 4 bilaterally equipped cochlear implant users was carried out to assess localization ability. Individuals in the bimodal implant group were all provided with the same type of hearing aid in the opposite ear, and subjects in the bilateral implant group used cochlear implants of the same manufacturer on each ear. Subjects adjusted the spot of a computer-controlled laser-pointer to the perceived direction of sound incidence in the frontal horizontal plane by rotating a trackball. Two subjects of the bimodal group who had substantial residual hearing showed localization ability in the bimodal configuration, whereas using each single device only the subject with better residual hearing was able to discriminate the side of sound origin. Five other subjects with more pronounced hearing loss displayed an ability for side discrimination through the use of bimodal aids, while four of them were already able to discriminate the side with a single device. Of the bilateral cochlear implant group one subject showed localization accuracy close to that of normal hearing subjects. This subject was also able to discriminate the side of sound origin using the first implanted device alone. The other three bilaterally equipped subjects showed limited localization ability using both devices. Among them one subject demonstrated a side-discrimination ability using only the first implanted device.