High sensitivity detectors for measurement of space potentialfluctuations

A detection technique yielding an order of magnitude increase in the sensitivity of a Proca-Green type energy analyzer to beam energy fluctuations has been demonstrated. A sensitivity of <1 part in 10 ⁶ is possible. The technique can be used to increase the sensitivity of a Heavy Ion Beam Probe (HIBP) to space potential fluctuations in a plasma. The increase in sensitivity is achieved by splitting the detected ion beam into 10 smaller beamlets and summing the signals produced by the beamlets. Experimental results from an ion beam test facility are presented along with the projected results if implemented on the 2 MeV HIBP on the TEXT-Upgrade tokamak     

High velocity dislocation motion and interatomic force law

The effect of the interatomic force law on the motion of a dislocation in a simple cubic crystal is investigated. Earlier work on the snapping bond model is extended to include a piecewise linear force law. Consistency conditions are obtained for atomic displacements that lie outside the range of Hooke's law (bond strain less than β). The conditions are solved analytically for small deviations from the snapping bond model [β ≈ ($\text{1}\text{2}$)] and numerically for a larger range of β. We obtain self consistent solutions for most of the dislocation velocity range. For ν > 0.7 the solutions do not differ markedly from those of the snapping bond model. For ν < 0.7 ther are noticeable deviations. The questions of the critical velocity at which breakdown will occur and of which bond is responsible are discussed.     

Laser induced fluorescence studies of iodine oxide chemistry. Part II. The reactions of IO with CH3O2, CF3O2 and O3

The technique of pulsed laser photolysis was coupled to laser induced fluorescence detection of iodine oxide (IO) to measure rate coefficients, k for the reactions IO + CH(3)O(2)--> products (R1, 30-318 Torr N(2)), IO + CF(3)O(2)--> products (R2, 70-80 Torr N(2)), and IO + O(3)--> OIO + O(2) (R3a). Values of k(1) = (2 +/- 1) x 10(-12) cm(3) molecule(-1) s(-1), k(2) = (3.6 +/- 0.8) x 10(-11) cm(3) molecule(-1) s(-1), and k(3a) <5 x 10(-16) cm(3) molecule(-1) s(-1) were obtained at T = 298 K. In the course of this work, the product yield of IO from the reaction of CH(3)O(2) with I was determined to be close to zero, whereas CH(3)OOI was formed efficiently at 70 Torr N(2). Similarly, no evidence was found for IO formation in the CF(3)O(2) + I reaction. An estimate of the rate coefficients k(CH(3)O(2) + I) = 2 x 10(-11) cm(3) molecule(-1) s(-1) and k(CH(3)OOI + I) = 1.5 x 10(-10) cm(3) molecule(-1) s(-1) was also obtained. The results on k(1)-k(3) are compared to the limited number of previous investigations and the implications for the chemistry of the marine boundary layer are briefly discussed.     

The Position Dependent 15N Enrichment of Nitrous Oxide in the Stratosphere

Abstract

The position dependent ¹⁵N fractionation of nitrous oxide (N₂O), which cannot be obtained from mass spectrometric analysis on molecular N₂O itself, can be determined with high precision using isotope ratio mass spectrometry on the NO⁺ fragment that is formed on electron impact in the source of an isotope ratio mass spectrometer. Laboratory UV photolysis experiments show that strong position dependent ¹⁵N fractionations occur in the photolysis of N₂O in the stratosphere, its major atmospheric sink. Measurements on the isotopic composition of stratospheric N₂O indeed confirm the presence of strong isotope enrichments, in particular the difference in the fractionation constants for ¹⁵N¹⁴NO and ¹⁴N¹⁵NO. The absolute magnitudes of the fractionation constants found in the stratosphere are much smaller, however, than those found in the lab experiments, demonstrating the importance of dynamical and also additional chemical processes like the reaction of N₂O with O(¹D).     

Oxygen isotope analysis of carbonates in the calcite-dolomite-magnesite solid-solution by high-temperature pyrolysis: initial results

Accurate and efficient measurement of the oxygen isotope composition of carbonates (delta(C) (18)O) based on the mass spectrometric analysis of CO(2) produced by reacting carbonate samples with H(3)PO(4) is compromised by: (1) uncertainties associated with fractionation factors (alpha(CO)(2)C) used to correct measured oxygen isotope values of CO(2)(delta(CO(2)(18)O) to delta(C) (18)O; and (2) the slow reaction rates of many carbonates of geological and environmental interest with H(3)PO(4). In contrast, determination of delta(C) (18)O from analysis of CO produced by high-temperature (>1400 degrees C) pyrolytic reduction, using an elemental analyser coupled to continuous-flow isotope-ratio mass spectrometry (TC/EA CF-IRMS), offers a potentially efficient alternative that measures the isotopic composition of total carbonate oxygen and should, therefore, theoretically be free of fractionation effects. The utility of the TC/EA CF-IRMS technique was tested by analysis of carbonates in the calcite-dolomite-magnesite solid-solution and comparing the results with delta(C) (18)O measured by conventional thermal decomposition/fluorination (TDF) on the same materials. Initial results show that CO yields are dependent on both the chemical composition of the carbonate and the specific pyrolysis conditions. Low gas yields (<100% of predicted yield) are associated with positive (>+0.2 per thousand) deviations in delta(C(TC/EA) (18)O compared with delta(C(TDF) (18)O. At a pyrolysis temperature of 1420 degrees C the difference between delta(C) (18)O measured by TC/EA CF-IRMS and TDF (Delta(C(TC/EA,TDF) (18)O) was found to be negatively correlated with gas yield (r = -0.785) and this suggests that delta(C) (18)O values (with an estimated combined standard uncertainty of +/-0.38 per thousand) could be derived by applying a yield-dependent correction. Increasing the pyrolysis temperature to 1500 degrees C also resulted in a statistically significant correlation with gas yield (r = -0.601), indicating that delta(C) (18)O values (with an estimated uncertainty of +/-0.43 per thousand) could again be corrected using a yield-dependent procedure. Despite significant uncertainty associated with TC/EA CF-IRMS analysis, the magnitude of the uncertainty is similar to that associated with the application of poorly defined values of alpha(CO)(2), (C) used to derive delta(C) (18)O from delta(CO(2) (18)O measured by the H(3)PO(4) method for most common carbonate phases. Consequently, TC/EA CF-IRMS could provide a rapid alternative for the analysis of these phases without any effective deterioration in relative accuracy, while analytical precision could be improved by increasing the number of replicate analyses for both calibration standards and samples. Although automated gas preparation techniques based on the H(3)PO(4) method (ISOCARB, Kiel device, Gas-Bench systems) have the potential to measure delta(CO)(2) (18)O efficiently for specific, slowly reacting phases (e.g. dolomite), problems associated with poorly defined alpha(CO)(2), (C) remain. The application of the Principle of Identical Treatment is not a solution to the analysis of these phases because it assumes that a single fractionation factor may be defined for each phase within a solid-solution regardless of its precise chemical composition. This assumption has yet to be tested adequately.     

An aqueous ammonia sensor based on an inkjet-printed polyaniline nanoparticle-modified electrode

A sensor for the amperometric detection of aqueous ammonia was fabricated using the inkjet printing of dodecylbenzene sulfonate (DBSA)-doped polyaniline nanoparticles (nanoPANI) onto a screen-printed carbon paste electrode. The combination of the environmentally inert, aqueous nanoparticle dispersion with the inkjet printing technique allowed the rapid fabrication of sensors based on polyaniline that was not easily achievable in the past due to the lack of processability of bulk forms of the conducting polymer. The resulting modified electrode was characterised with respect to its operating pH and number of print layers and was found to perform optimally at near neutral pH with four nanoPANI inkjet-printed layers. The sensor was tested in a flow injection system for its response to aqueous ammonia using amperometric detection at -0.3 V vs. Ag/AgCl pseudo-reference and was found to have reproducibility to injections of ammonia of below 5% RSD and good sensitivity with an experimental detection limit of 20 microM and a theoretical detection limit of 3.17 microM (0.54 ppm). The sensor was also tested for its day-to-day stability and its response towards a range of interferents common to refrigerant waste waters. This system allows the rapid production of an ultra-low-cost, solid state, polyaniline-based aqueous ammonia sensor.     

A switchable palladium-complexed molecular shuttle and its metastable positional isomers

We report the design, synthesis, characterization, and operation of a [2]rotaxane in which a palladium-complexed macrocycle can be translocated between 4-dimethylaminopyridine and pyridine monodentate ligand sites via reversible protonation, the metal remaining coordinated to the macrocycle throughout. The substitution pattern of the ligands and the kinetic stability of the Pd-N bond means that changing the chemical state of the thread does not automatically cause a change in the macrocycle's position in the absence of an additional input (heat and/or coordinating solvent/anion). Accordingly, under ambient conditions any of the four sets of protonated and neutral, stable, and metastable co-conformers of the [2]rotaxane can be selected, manipulated, isolated, and characterized.     

Protonmotive force: development of electrostatic drivers for synthetic molecular motors

Ferrocene has been investigated as a platform for developing protonmotive electrostatic drivers for molecular motors. When two 3-pyridine groups are substituted to the (rapidly rotating) cyclopentadienyl (Cp) rings of ferrocene, one on each Cp, it is shown that the (Cp) eclipsed, pi-stacked rotameric conformation is preferred both in solution and in the solid state. Upon quaternization of both of the pyridines substituents, either by protonation or by alkylation, it is shown that the preferred rotameric conformation is one where the pyridinium groups are rotated away from the fully pi-stacked conformation. Electrostatic calculations indicate that the rotation is caused by the electrostatic repulsion between the charges. Consistently, when the pi-stacking energy is increased pi-stacked population increases, and conversely when the electrostatic repulsion is increased pi-stacked population is decreased. This work serves to provide an approximate estimate of the amount of torque that the electrostatically driven ferrocene platform can generate when incorporated into a molecular motor. The overall conclusion is that the electrostatic interaction energy between dicationic ferrocene dipyridyl systems is similar to the pi-stacking interaction energy and, consequently, at least tricationic systems are required to fully uncouple the pi-stacked pyridine substituents.