Gas-phase deprotonation of arylalkylamines. A collision-induced dissociation study

The collision-induced dissociation (CID) of deprotonated arylalkylamines of general formula R(1)C(6)H(4)CHR(2)CH(2)NR(3)(2) (where R(1) = H, OH, F or NO(2); R(2) = H or OH; R(3) = H or CH(3)) generated by negative chemical ionization with H(2)O and D(2)O as ionizing reagents, is discussed. The negative chemical ionization mass spectra show that, in the absence of a hydroxy group in the aromatic ring, deprotonation takes place at the benzylic position whereas the proton is lost from the OH group when present. The nitro compound forms only M(-.) ions. The CID spectra of the deprotonated molecules show that fragmentations are strongly dependent on the structural features of the molecules, namely the presence or absence of substituents in the aromatic ring or aliphatic chain. Copyright 1999 John Wiley & Sons, Ltd.     

Native defect changes in cds single crystal platelets induced by vacuum heat treatments at temperatures up to 600°C

Physical properties of selected CdS single crystal platelets as-grown and after vacuum heat treatments at temperatures up to 600°C have been studied using u.v. excited edge emission, mass spectrometry, electrical resistivity and electron paramagnetic resonance (EPR). It was found that sulfur leaves the crystal at temperatures as low as 100°C creating a depletion layer. The native defect changes were monitored by edge emission studies at 4.2°K in combination with etch treatments. The defect structure throughout the crystal is not only dependent upon the temperature and atmosphere of the treatments, but is also strongly dependent upon the cooling rate.     

Correlation between implantation defects and dopants in Fe-implanted SiC

SiC single crystals were implanted with Fe ions and the effects of implantation temperature, Fe concentration, and subsequent swift heavy ion irradiation on both dopant and damage depth distributions were evaluated by using RBS and channelling techniques. It is found that an increase of the implantation temperature above the threshold temperature for amorphization can lead to the formation of a broad layer (∼50 nm) containing a large concentration of implanted Fe atoms (∼2 at.%) but almost free of implantation defects. This particular configuration is likely due to dynamic annealing during implantation combined with defect annihilation at the surface. It is only observed when the implanted species concentration does not exceed a critical value (which lies between 2 and 5 at.% in the present system). Post-implantation swift heavy ion irradiation leads to a further decrease of the damage level, while the Fe distribution is not affected. The Fe substitutional fraction has been evaluated in the different tested conditions. A maximum value of ∼50% is found when implantation is performed at the temperature above that required to prevent amorphization (470 K in the present system). Swift-heavy ion irradiation seems to induce Fe atoms relocation at substitutional positions.     

Novel H2 activation by a tris[3,5-bis(trifluoromethyl)phenyl]borane frustrated Lewis pair

Tris[3,5-bis(trifluoromethyl)phenyl]borane (1, BArF(18)), has been synthesised on a practical scale for the first time. According to the Gutmann-Beckett method it is a more powerful Lewis acid than B(C(6)F(5))(3). It forms a 'frustrated Lewis pair' with 2,2,6,6-tetramethylpiperidine which cleaves H(2) to form a salt containing the novel anion [μ-H(BArF(18))(2)](-).     

On-line coupling of size exclusion and capillary zone electrophoresis via a reversed-phase C18 trapping column for the analysis of structurally related enkephalins in cerebrospinal fluid

On-line coupled analytical techniques can be advantageous in the assay of smaller peptides in complex biological matrices such as plasma, cerebrospinal fluid (CSF) and tissues. The present study shows the feasibility of a recently developed system, consisting of a size-exclusion chromatographic (SEC) separation followed by a trapping procedure on an RP18 microcolumn with subsequent elution of the trapped fraction and separation by capillary zone electrophoresis (CZE) for the quantification of structural-related peptides in biological matrices, as demonstrated for a number of enkephalins in CSF. After SEC separation of the enkephalins from large proteins present in CSF a heart-cut of 200 nuL, containing the enkephalin peak, is taken, concentrated on the RP18 microcolumn and, after elution of the enkephalins with 80% acetonitrile, a fraction of the eluate is electrokinetically injected into the CZE system, where stacking and separation is achieved. The degradation of the peptides, caused by endogenous peptidases in the matrix, is sufficiently inhibited with imipramine HCl. The assay has a satisfactory linearity and intraday (9.70-16.3%) precision considering the complexity of this multidimensional separation system. The sensitivity of the method, with a concentration limit of quantification of 2.5 nug/mL, is comparable with other CZE assays for peptides and sufficient for the quantification of peptide drugs in biological matrices.     

A thin membrane artificial muscle rotary motor

Desirable rotary motor attributes for robotics include the ability to develop high torque in a low mass body and to generate peak power at low rotational speeds. Electro-active polymer artificial muscles offer promise as actuator elements for robotic motors. A promising artificial muscle technology for use as a driving mechanism for rotary motion is the dielectric elastomer actuator (DEA). We present a membrane DEA motor in which phased actuation of electroded sectors of the motor membrane impart orbital motion to a central drive that turns a rotor. The motor is inherently scalable, flexible, flat, silent in operation, amenable to deposition-based manufacturing approaches, and uses relatively inexpensive materials. As a membrane it can also form part of the skin of a robot. We have investigated the torque and power of stacked membrane layers. Specific power and torque ratios when calculated using active membrane mass only were 20.8 W/kg and 4.1 Nm/kg, respectively. These numbers compare favorably with a commercially available stepper motor.     

Stochastic coupled cluster theory

We describe a stochastic coupled cluster theory which represents excitation amplitudes as discrete excitors in the space of excitation amplitudes. Reexpressing the coupled cluster (CC) equations as the dynamics of excitors in this space, we show that a simple set of rules suffices to evolve a distribution of excitors to sample the CC solution and correctly evaluate the CC energy. These rules are not truncation specific and this method can calculate CC solutions to an arbitrary level of truncation. We present results of calculation on the neon atom, and nitrogen and water molecules showing the ability to recover both truncated and full CC results.