Raster microdiffraction with synchrotron radiation of hydrated biopolymers with nanometre step-resolution: case study of starch granules

X-ray radiation damage propagation is explored for hydrated starch granules in order to reduce the step resolution in raster-microdiffraction experiments to the nanometre range. Radiation damage was induced by synchrotron radiation microbeams of 5, 1 and 0.3?μm size with ～0.1?nm wavelength in B-type potato, Canna edulis and Phajus grandifolius starch granules. A total loss of crystallinity of granules immersed in water was found at a dose of ～1.3?photons?nm(-3). The temperature dependence of radiation damage suggests that primary radiation damage prevails up to about 120?K while secondary radiation damage becomes effective at higher temperatures. Primary radiation damage remains confined to the beam track at 100?K. Propagation of radiation damage beyond the beam track at room temperature is assumed to be due to reactive species generated principally by water radiolysis induced by photoelectrons. By careful dose selection during data collection, raster scans with 500?nm step-resolution could be performed for granules immersed in water.     

Nucleophilic reactivity of thiolate, hydroxide and phenolate ions towards a model O-arylated diazeniumdiolate prodrug in aqueous and cationic surfactant media

The kinetics of aromatic nucleophilic substitution of the nitric oxide‐generating diazeniumdiolate ion, DEA/NO, by thiols (L ‐glutathione, L ‐cysteine, DL ‐homocysteine, 1‐propanethiol, 2‐mercaptoethanol, and sodium thioglycolate) from the prodrug, DNP‐DEA/NO, has been examined in aqueous solution and in solutions of cationic DOTAP vesicles. Second‐order rate constants in buffered aqueous solutions (k_RS‐ = 3.48–30.9 M^?1 s^?1; 30 °C) gave a linear Brønsted plot (β_nuc = 0.414 ± 0.068) consistent with the rate‐limiting S_NAr nucleophilic attack by thiolate ions. Cationic DOTAP vesicles catalyze the thiolysis reactions with rate enhancements between 11 and 486‐fold in Tris‐HCl buffered solutions at pH 7.4. The maximum rate increase was obtained with thioglycolate ion. Thiolysis data are compared to data for nucleophilic displacement by phenolate (k_PhO‐ = 0.114 M^?1 s^?1) and hydroxide (k_OH‐ = 1.82 × 10^?2 M^?1 s^?1, 37 °C) ions. The base hydrolysis reaction is accelerated by CTAB micelles and DODAC vesicles, with the vesicles being ca 3‐fold more effective as catalysts. Analysis of the data using pseudo‐phase ion‐exchange (PIE) formalism implies that the rate enhancement of the thiolysis and base hydrolysis reactions is primarily due to reactant concentration in the surfactant pseudo‐phase. Copyright © 2009 John Wiley & Sons, Ltd.     

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.