No abstract

Herein, the reaction between CO(2) and piperidine, as well as commercially available functionalised piperidine derivatives, for example, those with methyl-, hydroxyl- and hydroxyalkyl substituents, has been investigated. The chemical reactions between CO(2) and the functionalised piperidines were followed in situ by using attenuated total reflectance (ATR) FTIR spectroscopy. The effect of structural variations on CO(2) absorption was assessed in relation to the ionic reaction products identifiable by IR spectroscopy, that is, carbamate versus bicarbonate absorbance, CO(2) absorption capacity and the mass-transfer coefficient at zero loading. On absorption of CO(2) , the formation of the carbamate derivatives of the 3- and 4-hydroxyl-, 3- and 4-hydroxymethyl-, and 4-hydroxyethyl-substituted piperidines were found to be kinetically less favourable than the carbamate derivatives of piperidine and the 3- and 4-methyl-substituted piperidines. As the CO(2) loading of piperidine and the 3- and 4-methyl- and hydroxyalkyl-substituted piperidines exceeded 0.5 moles of CO(2) per mole of amine, the hydrolysis of the carbamate derivative of these amines was observed in the IR spectra collected. From the subset of amines analysed, the 2-alkyl- and 2-hydroxyalkyl-substituted piperidines were found to favour bicarbonate formation in the reaction with CO(2) . Based on IR spectral data, the ability of these amines to form the carbamate derivatives was also established. Computational calculations at the B3LYP/6-31+G** and MP2/6-31+G** levels of theory were also performed to investigate the electronic/steric effects of the substituents on the reactivity (CO(2) capture performance) of different amines, as well as their carbamate structures. The theoretical results obtained for the 2-alkyl- and 2-hydroxyalkyl-substituted piperidines suggest that a combination of both the electronic effect exerted by the substituent and a reduction in the exposed area of the nitrogen atom play a role in destabilising the carbamate derivative and increasing its susceptibility to hydrolysis. A theoretical investigation into the structure of the carbamate derivatives of these amines revealed shorter NC bond lengths and a less-delocalised electron distribution in the carboxylate moiety.

The effects of the radiation emission on the motion of electrons in high-energy synchrotrons are analyzed. The damping rates and quantum excitation of the three principal modes of oscillation are derived for strong focusing and constant gradient accelerators. Methods for correcting the radiation effects for strong-focusing accelerators are discussed.

The two-dimensional spatial distribution of microdischarges in atmospheric pressure dielectric-barrier discharges (DBDs) in air was studied. Experimental images of DBDs (Lichtenberg figures) were obtained using photostimulable phosphors. The storage phosphor imaging method takes advantage of the linear response of the phosphor for characterization of microdischarge intensity and position. A microdischarge interaction model in DBDs is proposed and a Monte Carlo simulation of microdischarge interactions in the discharge is presented. Comparison of modelled and experimental images indicates interactions and short-range structuring of microdischarge channels.

Samples taken from the Dome C ice core, Antarctica, and the GRIP ice core, Greenland, are examined using the scanning electron microscope to determine their microstructure. In both cores, samples are taken from two differing climatic periods: the Holocene and the last glacial period. Many of the usual features observed in similar samples under the light microscope are observed, including: bubbles, grain boundaries and clathrate hydrates. Features not resolvable using the light microscope are also found. Dust particles are found in situ. Eighty-five per cent of those observed contained silicon, which was generally associated with aluminium and magnesium. An estimation is made of the relative proportions of dust particles located at grain boundaries and in the bulk of the ice grain. At Dome C a higher proportion than expected from a random distribution of particles was found located at grain boundaries, although in Greenland this was not found to be the case for most samples. Direct evidence is also presented indicating the role of dust particles and microscopical inclusions in impeding or ``pinning’’ grain-boundary migration. Soluble impurities are also detected at some triple junctions and grain boundaries.

Summary The microstructure and location of impurities in polar ice are of great relevance to ice core studies. We describe a reliable method to examine ice in the scanning electron microscope (SEM). Specimens were cut in a cold room and could have their surfaces altered by sublimation either before (pre‐etching) or after (etching) introduction to the cryo‐chamber of the SEM. Pre‐etching was used to smooth surfaces, whilst etching stripped away layers from the specimen surface, aiding the location of particles in situ, and allowing embedded structures to be revealed. X‐ray analysis was used to determine the composition of localized impurities, which in some cases had been concentrated on the surface by etching. Examining uncoated surfaces was found to be advantageous and did not detract from qualitative X‐ray analysis. Imaging uncoated was performed at low accelerating voltages and probe currents to avoid problems of surface charging.

Summary For the first time a scanned focused ion beam of approximately 50 nm diameter has been used to prepare biological material. Small defined areas of the surface were removed by ion etching to allow examination of the underlying structures with a scanning electron microscope. Different milling procedures were carried out on two anatomical features in mites of the genus Halarachne (Halarachnidae: Mesostigmata). In the first, square holes were milled into the surface of the peritrematal plate to reveal the structure of the underlying respiratory peritrematal groove. In the second, transverse cuts were made across the shafts of the sensory sensilli which make up the sensory Haller's organ on tarsus I. This latter procedure revealed detail both within the core and walls of sensilli. Details of specimen preparation and milling procedures, as well as suitability and interpretation of results, are presented.

No abstract