ALBERT

Notes: Abstract The main objective of this study was to analyse glycogen in single muscle fibres, using a recently developed microfluorometric method which detects subpicomol amounts of NADPH, glucose and glycogen (as glucosyl units) (detection limit 0.16–0.17pmol in a 25nl sample) without fluorochrome amplification. The fibres were freshly dissected from the twitch region of the iliofibularis muscle of the cane toad (Bufo marinus), and were mechanically skinned under paraffin oil to gain access to the intracellular compartments. The results show that: (1) glycogen concentrations in toad skeletal muscle fibres range between 25.8 and 369mmol glucosyl units/litre fibre volume; (2) there is a large variation in glycogen content between individual fibres from the iliofibularis muscle of one animal; (3) there are seasonal differences in the glycogen content of toad single muscle fibres; (4) the total amount of glycogen in single muscle fibres of the toad does not decrease significantly when storing the tissue, under paraffin oil, at 20–25°C for up to 6h or at 4°C for up to 24h; and (5) 15–26% of fibre glycogen can be washed in an aqueous solution at pH 5–7, within 5min, while 74–85% of fibre glycogen remains associated with the washed skinned fibre, even after 40min exposure of the skinned fibre preparation to the aqueous environment. The retention of most glycogen in the fibre preparation after mechanical removal of the plasma membrane and extensive washing indicates that in toad skeletal muscle fibres the largest proportion of glycogen is tightly bound to intracellular structures. The results also show that the skinned muscle fibre preparation is well suited for microfluorometric glycogen determination, since low molecular weight non-glycogen contributors to the fluorescence signal can be removed from the myoplasmic space prior to the glycogen hydrolysis step.

Notes: Calcsilicate granulites of probable Middle Proterozoic age (c.1000–1100 Ma) in the vicinity of Battye Glacier, northern Prince Charles Mountains, East Antarctica, contain prograde metamorphic assemblages comprising various combinations of wollastonite, scapolite, clinopyroxene, An-rich plagioclase, calcite, quartz, titanite and, rarely, orthoclase, ilmenite, phlogopite and graphite. Comparison of the prograde assemblages with calculated and experimentally determined phase relations in the simple CaO–Al2O3–SiO2–CO2–H2O system suggests peak metamorphism at ≥835 °C in the presence (in wollastonite-bearing assemblages at least) of a CO2-bearing fluid (XCO≥0.3) at a probable pressure of 6–7 kbar.Well-preserved retrograde reaction textures represent: (1) breakdown of scapolite to anorthite+calcite±quartz; (2) formation of grossular–andradite garnet and, locally, (3) epidote, both principally by reactions involving scapolite breakdown products and clinopyroxene; (4) local coupled replacement of clinopyroxene and ilmenite by hornblende and titanite, respectively; and finally (5) local sericitization of prograde and retrograde plagioclase. These retrograde reactions are interpreted to be the result of cooling and variable infiltration by H2O-rich fluids, possibly derived from crystallizing pegmatitic intrusions and segregations that may be partial melts, which are common throughout the area.

Notes: The Br2 fragment rotational distributions that result from the vibrational predissociation of NeBr2 in the B electronic state have been measured for several initial vibrational levels. In each case, the rotational distributions extend to the effective energetic limit determined by the amount of energy available (Eavl) for disposal into the fragment rotational and translational degrees of freedom. Analysis of the data allows refinement of the NeBr2 dissociation energy; we find that D0=70.0±1.1 cm−1 for the X electronic state, v=0. Both Δv=−1 and −2 dissociation events have been examined. For dissociation pathways with approximately the same value of Eavl the Δv=−2 pathways are observed to have a higher fraction of the fragment energy in rotational excitation. The overall shape of the Δv=−1 distributions are insensitive to the value of Eavl, suggesting that a Franck–Condon model for the dissociation may have some validity, though quantitative quantum mechanical calculations demonstrate that this model does not reproduce the large degree of fragment rotational excitation. Two classical models for the dissociation also fail to reproduce the extent of fragment rotational distribution. This result is discussed in light of previous experimental and theoretical investigations, focusing on the apparent agreement of classical models with the IBr fragment rotational distributions that result from the dissociation of NeIBr. © 1997 American Institute of Physics.

Notes: Recent electron diffraction and microscopy studies of GaN nucleation layers have shown that faults in the stacking of the close-packed planes result in the coexistence of cubic and hexagonal phases within the layers. Using grazing incidence x-ray scattering, we have quantified the proportion of the cubic and hexagonal phases throughout the nucleation layer. We compare the structure of a 20 nm nucleation layer grown on sapphire by atmospheric pressure metal-organic chemical vapor deposition at 525 °C to that of an identical layer heated to 1060 °C. The fractions of cubic and hexagonal phases in the layers are determined by a comparison of the scattering data with a Hendricks–Teller model. High temperature exposure results in a decrease of the cubic fraction from 0.56 to 0.17. The good agreement with the Hendricks–Teller model indicates that the positions of the stacking faults are uncorrelated. © 1998 American Institute of Physics.

Notes: We have investigated the quantification properties of scanning capacitance microscopy (SCM) by using two dedicated test structures and highlight the response of SCM to changes in dopant density. Our results indicate that contrast reversal occurs and that the SCM output is not always a monotonically increasing signal with decreasing dopant density. Two epitaxially grown staircase structures covering the doping ranges 1014–1020 cm−3 p type and 5×1014–5×1019 cm−3 n type were produced for this study as the turning point in the response function typically occurs at a doping level of around 1017 cm−3. Through the use of a simple simulation model we see that contrast reversal is expected due to a relative shift between the dC/dV curves for different doping levels. The onset of contrast reversal can be adjusted by changing the dc sample bias leading to a shift in the operating position of the SCM, and the significance of this point will be discussed here. © 1998 American Institute of Physics.

Notes: The filling processes of water and cyclohexane in porous silica (with a characteristic pore size of 60 Å) are investigated using the nuclear magnetic resonance (NMR) technique of cryoporometry. In this technique, the liquid was frozen in the pores before the temperature was raised gradually; melting the smallest particles first and then particles of increased size. The volume of the molten liquid present was measured using the height of a T2 spin echo. The experiments were performed with filling fractions ranging from 10% to 100%. The results showed distinctly different behaviors of the fluids, which depended on the surface adhesion. It was found that water (a fluid which wets the pore surface) forms small puddles—much smaller than the smallest pore size—at low filling fractions. These puddles grow in size as more water is added until all the pore volume is filled. Cyclohexane (a non-wetting fluid) on the other hand, does not form small puddles but completely fills the pores with a preference for the smaller pores. Water is found to give more accurate results for the pore size distribution than cyclohexane, in 60 Å silica. © 1998 American Institute of Physics.

Notes: The filling processes of water and cyclohexane in porous silica (40 Å, 60 Å and 112 Å pore size samples) were studied using T2 nuclear magnetic resonance (n.m.r.) experiments. The silica pores contained water or cyclohexane and the experiments were performed at room temperature and at filling fractions ranging from 0.02 to 1.0 (that is, completely full). Two distinct processes were observed which depended on the hydrophilicity of the silica surface (or the surface adhesion of the liquid). Water was found to collect in small puddles in the silica interstices, and to form a surface layer over the silica before the remaining pore volume was filled. Water in a surface-treated porous silica and cyclohexane in regular porous silica appeared to completely fill the smaller before the larger pores, and not form a separate surface-coating layer. This work also presents the techniques used to calculate quantitative information about the filling process; specifically, determination of the volume to surface-area ratio of the liquid puddles as well as the number of these puddles, is demonstrated. © 1997 American Institute of Physics.

Notes: The mechanism of the reaction CH4+O(1D2)→CH3+OH was investigated by ultrafast, time-resolved and state-resolved experiments. In the ultrafast experiments, short ultraviolet pulses photolyzed ozone in the CH4⋅O3 van der Waals complex to produce O(1D2). The ensuing reaction with CH4 was monitored by measuring the appearance rate of OH(v=0,1;J,Ω,Λ) by laser-induced fluorescence, through the OH A←X transition, using short probe pulses. These spectrally broad pulses, centered between 307 and 316 nm, probe many different OH rovibrational states simultaneously. At each probe wavelength, both a fast and a slow rise time were evident in the fluorescence signal, and the ratio of the fast-to-slow signal varied with probe wavelength. The distribution of OH(v,J,Ω,Λ) states, Pobs(v,J,Ω,Λ), was determined by laser-induced fluorescence using a high-resolution, tunable dye laser. The Pobs(v,J,Ω,Λ) data and the time-resolved data were analyzed under the assumption that different formation times represent different reaction mechanisms and that each mechanism produces a characteristic rovibrational distribution. The state-resolved and the time-resolved data can be fit independently using a two-mechanism model: Pobs(v,J,Ω,Λ) can be decomposed into two components, and the appearance of OH can be fit by two exponential rise times. However, these independent analyses are not mutually consistent. The time-resolved and state-resolved data can be consistently fit using a three-mechanism model. The OH appearance signals, at all probe wavelengths, were fit with times τfast(approximate)0.2 ps, τinter(approximate)0.5 ps and τslow(approximate)5.4 ps. The slowest of these three is the rate for dissociation of a vibrationally excited methanol intermediate (CH3OH*) predicted by statistical theory after complete intramolecular energy redistribution following insertion of O(1D2) into CH4. The Pobs(v,J,Ω,Λ) was decomposed into three components, each with a linear surprisal, under the assumption that the mechanism producing OH at a statistical rate would be characterized by a statistical prior. Dissociation of a CH4O* intermediate before complete energy randomization was identified as producing OH at the intermediate rate and was associated with a population distribution with more rovibrational energy than the slow mechanism. The third mechanism produces OH promptly with a cold rovibrational distribution, indicative of a collinear abstraction mechanism. After these identifications were made, it was possible to predict the fraction of signal associated with each mechanism at different probe wavelengths in the ultrafast experiment, and the predictions proved consistent with measured appearance signals. This model also reconciles data from a variety of previous experiments. While this model is the simplest that is consistent with the data, it is not definitive for several reasons. First, the appearance signals measured in these experiments probe simultaneously many OH(v,J,Ω,Λ) states, which would tend to obfuscate differences in the appearance rate of specific rovibrational states. Second, only about half of the OH(v,J,Ω,Λ) states populated by this reaction could be probed by laser-induced fluorescence through the OH A←X band with our apparatus. Third, the cluster environment might influence the dynamics compared to the free bimolecular reaction.

Notes: The collision-induced electronic energy transfer that occurs when I2 in the E(0g+) ion-pair electronic state collides with ground electronic state I2 has been investigated. We prepare I2 in single rotational levels in v=0 of the E state using two-color double resonance laser excitation. The resulting emission spectrum shows that the nearby (ΔTe=−385 cm−1) D(0u+) electronic state is populated. The cross section for collision-induced E→D energy transfer is found to be 18±3 Å2. A range of D state vibrational levels are populated, consistent with a model in which overlap between the initial and final vibrational wave functions is important, but modulated by propensities for small vibrational energy gaps and those energy gaps that are closely matched to the v=0→v=1 energy separation in the I2(X) collision partner. © 2001 American Institute of Physics.