Velocity map imaging of inelastic and elastic low energy electron scattering in organic nanoparticles.

Electron transport is of fundamental importance and has application in a variety of fields. Different scattering mechanisms affect electron transport in the condensed phase; hence, it is important to comprehensively understand these mechanisms and their scattering cross sections to predict electron transport properties. Whereas electron transport is well understood for high kinetic energy (KE) electrons, there is a discrepancy in the experimental and theoretical values for the Inelastic Mean Free Path (IMFP) in the low KE regime. In this work, velocity map imaging soft X-ray photoelectron spectroscopy is applied to unsupported organic nanoparticles (squalene) to extract experimental values of inelastic and elastic mean free paths (EMFPs). The obtained data are used to calculate corresponding scattering cross sections. The data demonstrate a decrease in the IMFP and increase in the EMFP with increasing electron KE between 10 and 50 eV.

Key drivers of cloud response to surface-active organics.

Aerosol-cloud interactions constitute the largest source of uncertainty in global radiative forcing estimates, hampering our understanding of climate evolution. Recent empirical evidence suggests surface tension depression by organic aerosol to significantly influence the formation of cloud droplets, and hence cloud optical properties. In climate models, however, surface tension of water is generally assumed when predicting cloud droplet concentrations. Here we show that the sensitivity of cloud microphysics, optical properties and shortwave radiative effects to the surface phase are dictated by an interplay between the aerosol particle size distribution, composition, water availability and atmospheric dynamics. We demonstrate that accounting for the surface phase becomes essential in clean environments in which ultrafine particle sources are present. Through detailed sensitivity analysis, quantitative constraints on the key drivers - aerosol particle number concentrations, organic fraction and fixed updraft velocity - are derived for instances of significant cloud microphysical susceptibilities to the surface phase.

Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth.

Mystery surrounds the transition from gas-phase hydrocarbon precursors to terrestrial soot and interstellar dust, which are carbonaceous particles formed under similar conditions. Although polycyclic aromatic hydrocarbons (PAHs) are known precursors to high-temperature carbonaceous-particle formation, the molecular pathways that initiate particle formation are unknown. We present experimental and theoretical evidence for rapid molecular clustering-reaction pathways involving radicals with extended conjugation. These radicals react with other hydrocarbon species to form covalently bound complexes that promote further growth and clustering by regenerating resonance-stabilized radicals through low-barrier hydrogen-abstraction and hydrogen-ejection reactions. Such radical-chain reaction pathways may lead to covalently bound clusters of PAHs and other hydrocarbons that would otherwise be too small to condense at high temperatures, thus providing the key mechanistic steps for rapid particle formation and surface growth by hydrocarbon chemisorption.

Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals.

The heterogeneous oxidation of organic aerosol by hydroxyl radicals (OH) can proceed through two general pathways: functionalization, in which oxygen functional groups are added to the carbon skeleton, and fragmentation, in which carbon-carbon bonds are broken, producing higher volatility, lower molecular weight products. An ongoing challenge is to develop a quantitative molecular description of these pathways that connects the oxidative evolution of the average aerosol properties (e.g. size and hygroscopicity) to the transformation of free radical intermediates. In order to investigate the underlying molecular mechanism of aerosol oxidation, a relatively compact kinetics model is developed for the heterogeneous oxidation of squalane particles by OH using free radical intermediates that convert reactive hydrogen sites into oxygen functional groups. Stochastic simulation techniques are used to compare calculated system properties over ten oxidation lifetimes with the same properties measured in experiment. The time-dependent average squalane aerosol mass, volume, density, carbon number distribution of scission products, and the average elemental composition are predicted using known rate coefficients. For functionalization, the calculations reveal that the distribution of alcohol and carbonyl groups is controlled primarily by the initial OH abstraction rate and to lesser extent by the branching ratio between secondary peroxy radical product channels. For fragmentation, the calculations reveal that the formation of activated alkoxy radicals with neighboring functional groups controls the molecular decomposition, particularly at high O/C ratios. This kinetic scheme provides a framework for understanding the oxidation chemistry of a model organic aerosol and informs parameterizations of more complex systems.

Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake.

An accurate description of the evolution of organic aerosol in the Earth's atmosphere is essential for climate models. However, the complexity of multiphase chemical and physical transformations has been challenging to describe at the level required to predict aerosol lifetimes and changes in chemical composition. In this work a model is presented that reproduces experimental data for the early stages of oxidative aging of squalane aerosol by hydroxyl radical (OH), a process governed by reactive uptake of gas phase species onto the particle surface. Simulations coupling free radical reactions and Fickian diffusion are used to elucidate how the measured uptake coefficient reflects the elementary steps of sticking of OH to the aerosol as a result of a gas-surface collision, followed by very rapid abstraction of hydrogen and subsequent free radical reactions. It is found that the uptake coefficient is not equivalent to a sticking coefficient or an accommodation coefficient: it is an intrinsically emergent process that depends upon particle size, viscosity, and OH concentration. An expression is derived to examine how these factors control reactive uptake over a broad range of atmospheric and laboratory conditions, and is shown to be consistent with simulation results. Well-mixed, liquid behavior is found to depend on the reaction conditions in addition to the nature of the organic species in the aerosol particle.

Competitive reaction pathways for functionalization and volatilization in the heterogeneous oxidation of coronene thin films by hydroxyl radicals and ozone.

X-ray photoelectron spectroscopy (XPS) is used to monitor the heterogeneous reaction of hydroxyl radicals (OH) and ozone with thin films (∼5 Å) of coronene. Detailed elemental and functional group analysis of the XPS spectra reveals that there is a competition between the addition of oxygenated functional groups (functionalization) and the loss of material (volatilization) to the gas phase. Measurements of the film thickness and elemental composition indicate that carbon loss is as important as the formation of new oxygenated functional groups in controlling how the oxygen-to-carbon ratio (O/C) of the coronene film evolves during the surface reaction. When the O/C ratio of the film is small (∼0.1) the addition of functional groups dominates changes in film thickness, while for more oxygenated films (O/C > 0.3) carbon loss is an increasingly important reaction pathway. Decomposition of the film occurs via the loss of both carbon and oxygen atoms when the O/C ratio of the film exceeds 0.5. These results imply that chemically reduced hydrocarbons, such as primary organic aerosol, age in the atmosphere by forming new oxygenated functional groups, in contrast to oxygenated secondary organic aerosol, which decompose by a heterogeneous loss of carbon and/or oxygen.

Evolution of organic aerosols in the atmosphere.

Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework describing the atmospheric evolution of OA that is constrained by high-time-resolution measurements of its composition, volatility, and oxidation state. OA and OA precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. Our model framework captures the dynamic aging behavior observed in both the atmosphere and laboratory: It can serve as a basis for improving parameterizations in regional and global models.

Temporal integration limits of stereovision in reaching and grasping.

Even though there have been extensive investigations of the temporal integration limits of binocular vision in perceptual tasks, relatively little is known about temporal integration limits during the completion of visuomotor tasks. To assess the temporal integration limits of binocular disparity within the action domain, accuracy of reach kinematics in a reaching and grasping task under continuous binocular and monocular viewing conditions were compared with those obtained under alternating monocular viewing conditions with interocular delays ranging from 14 to 58 ms. Even the shortest of the interocular delays resulted in larger grip apertures than those in the continuous monocular and binocular viewing conditions. The short temporal integration interval of stereovision obtained in this study cannot be accounted for by differential visual feedback in the binocular and interocular delay conditions, nor is it likely to be a consequence of visual disruption due to the interocular delays. Our findings suggest that the visuomotor system has little tolerance to interocular delay.

Effects of 2-hydroxy-4-(methylthio)-butanoic acid on performance and carcass characteristics of finishing beef cattle and on fermentation in continuous culture.

Three experiments were conducted to evaluate the effects of feeding 2-hydroxy-4- (methylthio)-butanoic acid (HMTBA) on performance and carcass characteristics of feedlot cattle and on microbial fermentation in a continuous-culture system. In Exp. 1, 160 crossbred steers (initial BW = 385 +/- 10.3 kg) were assigned to 4 treatments consisting of control (0% HMTBA) or 3 diets containing HMTBA (0.069, 0.137, and 0.204%; DM basis) in a randomized complete block design. As the percent of HMTBA increased in the diet, final BW (P = 0.069), final BW adjusted to a constant dressing percent (P = 0.063), and overall ADG (P = 0.099) tended to decrease linearly. Overall DMI decreased linearly (P < or = 0.006) with increasing HMTBA dose. No differences (P > or = 0.10) were noted for carcass characteristics, except for a tendency (P = 0.078) for a linear increase in the percentage of cattle grading USDA Choice with increasing HMTBA dose. In Exp. 2, 80 crossbred steers (initial BW = 450 +/- 17 kg) in a randomized complete block design were assigned to a control (0% HMTBA) diet or to a diet in which the concentrations of HMTBA were gradually increased from 0.036 to 0.212% of DM over a 50-d period. The HMTBA-containing diet tended to decrease DMI (P = 0.132), but G:F (P = 0.319) for the overall feeding period, carcass measurements, and USDA quality grade (P > or = 0.149) did not differ between treatments. In Exp. 3, continuous culture fermenters (n = 5/treatment) were used to determine the effects of HMTBA (control vs. 0.24% HMTBA) on microbial fermentation. No differences (P > or = 0.31) were detected between treatments in ruminal OM digestibility, microbial N synthesis, pH, ammonia, molar proportions of VFA, or effluent concentration of selected long-chain fatty acids. These results suggest that HMTBA decreased DMI by feedlot steers fed a steam-flaked corn-based diet in a dose-dependent manner; however, gradually increasing the dose over time seemed to moderate effects on DMI. No major changes in microbial fermentation in continuous culture were observed with HMTBA at 0.24% of dietary DM, suggesting effects of HMTBA on DMI were not likely associated with changes in ruminal digestion or fermentation.

Effects of ractopamine hydrochloride on performance, rate and variation in feed intake, and acid-base balance in feedlot cattle.

Two experiments evaluated effects of ractopamine hydrochloride (RAC) on performance, intake patterns, and acid-base balance of feedlot cattle. In Exp. 1, 360 crossbred steers (Brangus, British, and British x Continental breeding; initial BW = 545 kg) were used in a study with a 3 x 3 factorial design to study the effects of dose [0, 100, or 200 mg/(steer x d) of RAC] and duration (28, 35, or 42 d) of feeding of RAC in a randomized complete block design (9 treatments, 8 pens/treatment). No dose x duration interactions were detected (P > 0.10). As RAC dose increased, final BW (FBW; P = 0.01), ADG (P < 0.01), and G:F (P < 0.01) increased linearly. As duration of feeding increased, ADG increased quadratically (P = 0.04), with tendencies for quadratic effects for FBW (P = 0.06), DMI (P = 0.07), and G:F (P = 0.09). Hot carcass weight increased linearly (P = 0.02) as dose of RAC increased. Thus, increasing the dose of RAC from 0 to 200 mg/(steer x d) and the duration of feeding from 28 to 42 d improved feedlot performance, although quadratic responses for duration of feeding indicated little improvement as the duration was extended from 35 to 42 d. In Exp. 2, 12 crossbred beef steers (BW = 593 kg) were used in a completely random design to evaluate the effects of RAC [0 or 200 mg/(steer x d) for 30 d; 6 steers/treatment] on rate of intake, daily variation in intake patterns, and acid-base balance. To assess intake patterns, absolute values of daily deviations in feed delivered to each steer relative to the total quantity of feed delivered were analyzed as repeated measures. There were no differences (P > 0.10) in feedlot performance, urine pH, blood gas measurements, or variation in intake patterns between RAC and control cattle, but steers fed RAC had increased (P = 0.04) LM area, decreased (P = 0.03) yield grade, and increased (P < 0.10) time to consume 50 and 75% of daily intake relative to control steers. Our results suggest that feeding RAC for 35 d at 200 mg/(steer x d) provided optimal performance, and no effects on acid-base balance or variation in intake patterns of finishing steers were noted with RAC fed at 200 mg/(steer x d) over a 30-d period.

Overview of endogenous and synthetic melanocortin peptides.

The melanocortin system consists of five seven-transmembrane spanning G-protein coupled (GPCRs) receptors (MC1R-MC5R), the endogenous agonists a-, B- and melanocyte stimulating hormone (MSH), adrenocorticotropic hormone (ACTH), and the endogenous antagonists Agouti and Agouti-related protein (AGRP). Melanocortin agonists are involved in the regulation of feeding behavior and weight omeostasis in mammals. Structure-activity relationships (SAR) have been performed on the endogenous melanocortin receptor agonists and antagonists that have identified ligand amino acid residues implicated as important for receptor binding and stimulation. Knowledge of putative ligand-receptor interactions may help to design molecules as therapeutic agents for the treatment of physiological diseases.

pH dependence of the electronic structure of glycine.

The carbon, nitrogen, and oxygen K-edge spectra were measured for aqueous solutions of glycine by total electron yield near-edge X-ray absorption fine structure (TEY NEXAFS) spectroscopy. The bulk solution pH was systematically varied while maintaining a constant amino acid concentration. Spectra were assigned through comparisons with both previous studies and ab initio computed spectra of isolated glycine molecules and hydrated glycine clusters. Nitrogen K-edge solution spectra recorded at low and moderate pH are nearly identical to those of solid glycine, whereas basic solution spectra strongly resemble those of the gas phase. The carbon 1s --> pi*(C=O) transition exhibits a 0.2 eV red shift at high pH due to the deprotonation of the amine terminus. This deprotonation also effects a 1.4 eV red shift in the nitrogen K-edge at high pH. Two sharp preedge features at 401.3 and 402.5 eV are also observed at high pH. These resonances, previously observed in the vapor-phase ISEELS spectrum of glycine, have been reassigned as transitions to sigma* bound states. The observation of these peaks indicates that the amine moiety is in an acceptor-only hydrogen bond configuration at high pH. At low pH, the oxygen 1s --> pi*(C=O) transition exhibits a 0.25-eV red shift due to the protonation of the carboxylic acid terminus. These spectral differences indicate that the variations in electronic structure observed in the NEXAFS spectra are determined by the internal charge state and hydration environment of the molecule in solution.

Interpersonal variability in dependent personality.

The interpersonal circumplex (IPC) was recommended as a personality trait dimensional model with good potential to identify the phenomenological scope of personality disorders whose core dysfunction involves maladaptive expression of interpersonal traits. The IPC was then applied to the reconceptualization of dependent personality and dependent personality disorder. In Study 1, Pincus and Gurtman's (1995) three interpersonal vectors of dependency were validated via factor analyses conducted on two large samples (N = 921; N = 472) and a reliable self-report measure, the 3 Vector Dependency Inventory (3VDI) was constructed. In Study 2, two samples (N = 103; N = 122) of individuals identified as predominantly endorsing submissive dependence, exploitable dependence, or love dependence, or who were low in aspects of dependency were compared via ANOVA and chi-square analyses on parental representations, adult attachment styles, loneliness, and pathological attachment. Submissive dependence was associated with higher scores on maladaptive constructs (fearful attachment, pathological attachment, and loneliness) and was also associated with lower parental affiliation and higher maternal control. Love dependence was associated with lower scores on maladaptive constructs and higher scores on secure attachment and parental affiliation. Variability in dependent phenomenology was related to its three component traits. Multiple perspectives on integrating love dependence, exploitable dependence, and submissive dependence into a reconceptualization of dependent personality disorder were articulated.

Anharmonic lattice dynamics in germanium measured with ultrafast x-ray diffraction.

Damping of impulsively generated coherent acoustic oscillations in a femtosecond laser-heated thin germanium film is measured as a function of fluence by means of ultrafast x-ray diffraction. By simultaneously measuring picosecond strain dynamics in the film and in the unexcited silicon substrate, we separate anharmonic damping from acoustic transmission through the buried interface. The measured damping rate and its dependence on the calculated temperature of the thermal bath is consistent with estimated four-body, elastic dephasing times (T2) for 7-GHz longitudinal acoustic phonons in germanium.

Two-photon image correlation spectroscopy and image cross-correlation spectroscopy.

We introduce two-photon image correlation spectroscopy (ICS) using a video rate capable multiphoton microscope. We demonstrate how video rate two-photon microscopic imaging and image correlation analysis may be combined to measure molecular transport properties over ranges typical of biomolecules in membrane environments. Using two-photon ICS, we measured diffusion coefficients as large as 10(-8) cm2 s(-1) that matched theoretical predictions for samples of fluorescent microspheres suspended in aqueous sucrose solutions. We also show the sensitivity of the method for measuring microscopic flow using analogous test samples. We demonstrate explicitly the advantages of the image correlation approach for measurement of correlation functions with high signal-to-noise in relatively short time periods and discuss situations when these methods represent improvements over non-imaging fluorescence correlation spectroscopy. We present the first demonstration of two-photon image cross-correlation spectroscopy where we simultaneously excite (via two-photon absorption) non-identical fluorophores with a single pulsed laser. We also demonstrate cellular application of two-photon ICS for measurements of slow diffusion of green fluorescent protein/adhesion receptor constructs within the basal membrane of live CHO fibroblast cells.

Lateral diffusion of membrane proteins in the presence of static and dynamic corrals: suggestions for appropriate observables.

We consider the possibility of inferring the nature of cytoskeletal interaction with transmembrane proteins via optical experiments such as single-particle tracking (SPT) and near-field scanning optical microscopy (NSOM). In particular, we demonstrate that it may be possible to differentiate between static and dynamic barriers to diffusion by examining the time-dependent variance and higher moments of protein population inside cytoskeletal "corrals." Simulations modeling Band 3 diffusion on the surface of erythrocytes provide a concrete demonstration that these statistical tools might prove useful in the study of biological systems.

Regulation of protein mobility in cell membranes: a dynamic corral model.

We analyze a two-state stochastic corral model for regulation of protein diffusion in a cell membrane. This model could mimic control of protein transport in the membrane by the cytoskeleton. The dynamic corral acts as a gate which when open permits an otherwise trapped protein to escape to a neighboring corral in the cytoskeletal network. We solve for the escape rate over a wide range of parameters of the model, and compare these results with Monte Carlo simulations. Upon introducing measured values of the model parameters for Band 3 in erythrocyte membranes, we are able to estimate the value for one unknown parameter, the average rate at which the corral closes. The ratio of calculated closing rate to measured opening rate is roughly 100:1, consistent with a gating mechanism whereby protein mobility is regulated by dissociation and reassociation of segments of the cytoskeletal network.

Detection of nonthermal melting by ultrafast X-ray diffraction.

Using ultrafast, time-resolved, 1.54 angstrom x-ray diffraction, thermal and ultrafast nonthermal melting of germanium, involving passage through nonequilibrium extreme states of matter, was observed. Such ultrafast, optical-pump, x-ray diffraction probe measurements provide a way to study many other transient processes in physics, chemistry, and biology, including direct observation of the atomic motion by which many solid-state processes and chemical and biochemical reactions take place.

Probing microscopic chemical environments with high-intensity chirped pulses.

By varying the chirp of high-intensity pulses, we can use the chirp-condition-dependent fluorescence yield to distinguish among different molecules or the same molecule in different microenvironments. As an example of the latter we show that SNAFL-2, a well-known pH-sensitive dye, shows large modulation in fluorescence yield in response to both variation in acidity and variation in chirp condition. Future application of this technique as a novel contrast mechanism within fluorescence microscopy is discussed.

Third-harmonic generation microscopy by use of a compact, femtosecond fiber laser source.

We demonstrate the first use, to our knowledge, of a compact, diode-pumped, femtosecond fiber laser for third-harmonic generation (THG) microscopy. We discuss the utility of this technique, as well as the technical issues involved in using this compact source, and demonstrate the first use, to our knowledge, of imaging by THG backlighting.