Asymmetric syntheses of dihydroxyhomoprolines via doubly diastereoselective lithium amide conjugate addition reactions

The asymmetric syntheses of novel dihydroxyhomoprolines have been achieved using the doubly diastereoselective conjugate additions of the antipodes of lithium N-benzyl-N-(α-methylbenzyl)amide to a set of four chiral α,β-unsaturated esters (derived from d-pentoses) as one of the key steps. A full account of the diastereoselectivity observed in these conjugate additions is presented and the stereochemical outcomes of these reactions have been established unambiguously via a combination of hydrogenolytic chemical correlation and single crystal X-ray diffraction analyses. A tandem hydrogenolysis/intramolecular reductive amination reaction was then used to create the corresponding enantiopure pyrrolidines, providing access to (2′S,3′S,4′R)-dihydroxyhomoproline and (2′S,3′R,4′S)-dihydroxyhomoproline after deprotection.     

The production and destruction of the C-related 969 meV absorption band in Si

Data are reported on the production of the 969 meV absorption line as functions of the carbon concentration and radiation dose in FZ and CZ silicon. With increasing dose of 2 MeV electrons the absorption first increases and then decreases. Simple equations are presented which describe the growth and decay. It is shown that, in favourable circumtances, carbon concentrations as low as 10¹⁴ cm⁻³ can be detected in silicon by means of the 969 meV absorption line. We verify that the 969 meV line anneals out at temperatures >500 K but may increase between 450 and 500 K. We show that the increase is largest in samples irradiated at room temperature to a small dose relative to the carbon concentration.     

Optimizing phase imaging via dynamic force curves

Tapping mode (TM, also called intermittent contact mode) atomic force microscopy (AFM) has been routinely used in many laboratories. However, consistent or deliberate control of measuring conditions and interpretation of results are often difficult. In this article, we demonstrate how measurement parameters (drive frequency, cantilever stiffness and oscillation amplitude) affect the tapping tip's state. This has been done by systematic dynamic force measurements performed on mica and polystyrene surfaces together with computer simulations. Our study shows the following results. (1) Weaker cantilevers, smaller amplitude and higher drive frequency (around the resonance) lead to an extension of the attractive region (greater phase lag) in amplitude–phase–distance curves and thus can help to achieve stable high-setpoint TM imaging with minimal tip–sample pressure. (2) Bistability of tapping tips often exists and may cause height artefacts if the setpoint falls in the bistable region. (3) Tapping tips with high vibrating energy (stiff cantilevers and large amplitude) driven at resonance are only slightly perturbed by tip–sample interactions and usually remain monostable during the sweep of the scanner position. This can help to achieve good phase contrast without significant artefacts when the setpoint falls in a continuous negative–positive phase shift transition region. (4) Low energy cantilevers (compliant cantilevers and small amplitude) usually result in large phase shift and can be used to acquire large phase contrast images. However, height artefacts will occur when the setpoint falls in the bistable region usually existing for such cantilevers. (5) Computer simulations are useful in understanding the bistability in dynamic force curves and determining either material properties or the optimal imaging parameters.     

Diagnostic studies of molecular plasmas using mid-infrared semiconductor lasers

Within the last decade mid-infrared absorption spectroscopy between 3 and 20 μm, known as infrared laser absorption spectroscopy (IRLAS) and based on tuneable semiconductor lasers, namely lead salt diode lasers, often called tuneable diode lasers (TDL), and quantum cascade lasers (QCL) has progressed considerably as a powerful diagnostic technique for in situ studies of the fundamental physics and chemistry of molecular plasmas. The increasing interest in processing plasmas containing hydrocarbons, fluorocarbons, organo-silicon and boron compounds has lead to further applications of IRLAS because most of these compounds and their decomposition products are infrared active. IRLAS provides a means of determining the absolute concentrations of the ground states of stable and transient molecular species, which is of particular importance for the investigation of reaction kinetics. Since plasmas with molecular feed gases are used in many applications such as thin film deposition, semiconductor processing, surface activation and cleaning, and materials and waste treatment, this has stimulated the adaptation of infrared spectroscopic techniques to industrial requirements. The recent development of QCLs offers an attractive new option for the monitoring and control of industrial plasma processes as well as for highly time-resolved studies on the kinetics of plasma processes. The aim of the present article is twofold: (i) to review recent achievements in our understanding of molecular phenomena in plasmas using TDLs and (ii) to report on selected new applications of QCLs in the mid-infrared. PACS  07.57.Ty; 52.70.Kz; 52.80.-s     

Quantum stochastic processes II

We investigate properties of a class of quantum stochastic processes subject to a condition of irreducibility. These processes must be recurrent or transient and an equilibrium state can only exist in the former case. Every finite dimensional process is recurrent and it is possible to establish convergence in time to a unique equilibrium state. We study particularly the class of transition processes, which describe photon emissions of simple quantum mechanical systems in excited states.Work supported by U.S.A.F. contract number F 44620-67-C-0029.     

Analysis of the absorption mechanism during laser-metal interaction

The present study examines the absorption of a laser beam at different wavelengths by a partially-ionized vapour during the interaction mechanism. The applicability of the theoretical models developed is discussed in detail. The interaction of the high- and low-power intensities of a laser beam with plasma is distinguished. It is shown that different metal vapours at similar temperatures and densities have absorption depths which may differ by an order of magnitude. Even more substantial is the difference between the absorption depths of light from different lasers in common use. It is also shown that the free electron temperature becomes significantly different from the heavy particle temperature for power intensities above the critical level which is typically > 10¹⁴W/m². The free electron velocity distribution has an isotropic part which becomes non-Maxwellian for power intensities greater than the critical power intensity.     

Pitman closeness results for Type-I censored data from exponential distribution

Recent work on Pitman closeness has compared estimators under Type-II censored samples from exponential distribution based on observed number of failures. In this paper, we carry out similar Pitman closeness comparisons for Type-I censored samples from exponential distribution based on time under test.     

Experimental and modeling studies of B atom number density distributions in hot filament activated B2H6/H2 and B2H6/CH4/H2 gas mixtures

Experimental and modeling studies of the gas-phase chemistry occurring in dilute, hot filament (HF) activated B2H6/H2 and B2H6/CH4/H2 gas mixtures are reported. Spatially resolved relative number densities of B (and H) atoms have been measured by resonance enhanced multiphoton ionization methods, as a function of process conditions (e.g. the HF material and its temperature, the B2H6/H2 mixing ratio, and the presence (or not) of added CH4). Three-dimensional modeling of the H/B chemistry prevailing in such HF activated gas mixtures using a simplified representation of the gas phase chemistry succeeds in reproducing all of the experimentally observed trends, and in illustrating the key role of the "H-shifting" reactions BHx + H <= => BHx-1 + H2 (x = 1-3) in enabling rapid interconversion between the various BHx (x = 0-3) species. CH4 addition, at partial pressures appropriate for growth of boron-doped diamond by chemical vapor deposition methods, leads to approximately 30% reduction in the measured B atom signal near the HF. The modeling suggests that this is mainly due to concomitant H atom depletion near the HF, but it also allows us a first assessment of the possible contributions from B/C coupling reactions upon CH4 addition to HF activated B2H6/H2 gas mixtures.