Enzyme kinetics for a two-step enzymic reaction with comparable initial enzyme-substrate ratios

We extend the validity of the quasi-steady state assumption for a model double intermediate enzyme-substrate reaction to include the case where the ratio of initial enzyme to substrate concentration is not necessarily small. Simple analytical solutions are obtained when the reaction rates and the initial substrate concentration satisfy a certain condition. These analytical solutions compare favourably with numerical solutions of the full system of differential equations describing the reaction. Experimental methods are suggested which might permit the application of the quasi-steady state assumption to reactions where it may not have been obviously applicable before

Electronic transport in films of colloidal CdSe nanocrystals

We present results for electronic transport measurements on large three-dimensional arrays of CdSe nanocrystals. In response to a step in the applied voltage, we observe a power-law decay of the current over five orders of magnitude in time. Furthermore, we observe no steady-state dark current for fields up to 10^6 V/cm and times as long as 2x10^4 seconds. Although the power-law form of the decay is quite general, there are quantitative variations with temperature, applied field, sample history, and the material parameters of the array. Despite evidence that the charge injected into the film during the measurement causes the decay of current, we find field-scaling of the current at all times. The observation of extremely long-lived current transients suggests the importance of long-range Coulomb interactions between charges on different nanocrystals.Comment: 11 pages, 10 figure

Disseminated Effects in Agent Based Models: A Potential Outcomes Framework and Application to Inform Pre-Exposure Prophylaxis Coverage Levels for HIV Prevention

Pre-exposure prophylaxis (PrEP) for HIV prevention may not only benefit the individual who uses it, but also their uninfected sexual risk contacts. We developed an agent-based model using a novel trial emulation approach to quantify disseminated effects of PrEP use among men who have sex with men in Atlanta, USA from 2015 to 2017. Components (subsets of agents connected through partnerships in a sexual network, but not sharing partnerships with any other agents) were first randomized to an intervention coverage level or control, then within intervention components, eligible agents were randomized to PrEP. We estimated direct and disseminated (indirect) effects using randomization-based estimators and reported corresponding 95% simulation intervals across scenarios ranging from 10% to 90% coverage in the intervention components. A population of 11,245 agents was simulated with an average of 1,551 components identified. Comparing agents randomized to PrEP in 70% coverage components to control agents, there was a 15% disseminated risk reduction in HIV incidence (95% simulation intervals = 0.65, 1.05). Individuals not on PrEP may receive a protective benefit by being in a sexual network with higher PrEP coverage. Agent-based models are useful to evaluate possible direct and disseminated effects of HIV prevention modalities in sexual networks

Predicting local and non-local effects of resources on animal space use using a mechanistic step selection model

1. Predicting space use patterns of animals from their interactions with the environment is fundamental for understanding the effect of habitat changes on ecosystem functioning. Recent attempts to address this problem have sought to unify resource selection analysis, where animal space use is derived from available habitat quality, and mechanistic movement models, where detailed movement processes of an animal are used to predict its emergent utilization distribution. Such models bias the animal's movement towards patches that are easily available and resource-rich, and the result is a predicted probability density at a given position being a function of the habitat quality at that position. However, in reality, the probability that an animal will use a patch of the terrain tends to be a function of the resource quality in both that patch and the surrounding habitat. 2. We propose a mechanistic model where this non-local effect of resources naturally emerges from the local movement processes, by taking into account the relative utility of both the habitat where the animal currently resides and that of where it is moving. We give statistical techniques to parametrize the model from location data and demonstrate application of these techniques to GPS data of caribou in Newfoundland. 3. Steady-state animal probability distributions arising from the model have complex patterns that cannot be expressed simply as a function of the local quality of the habitat. In particular, large areas of good habitat are used more intensively than smaller patches of equal quality habitat, whereas isolated patches are used less frequently. 4. Whilst we focus on habitats in this study, our modelling framework can be readily used with any environmental covariates and therefore represents a unification of mechanistic modelling and step selection approaches to understanding animal space use

Study of heterogeneous nucleation of eutectic Si in high-purity Al-Si alloys with Sr addition

The official published version can be accessed from the link below - Copyright @ 2010 The Minerals, Metals & Materials Society and ASM InternationalAl-5 wt pct Si master-alloys with controlled Sr and/or P addition/s were produced using super purity Al 99.99 wt pct and Si 99.999 wt pct materials in an arc melter. The master-alloy was melt-spun resulting in the production of thin ribbons. The Al matrix of the ribbons contained entrained Al-Si eutectic droplets that were subsequently investigated. Differential scanning calorimetry, thermodynamic calculations, and transmission electron microscopy techniques were employed to examine the effect of the Sr and P additions on eutectic undercoolings and nucleation phenomenon. Results indicate that, unlike P, Sr does not promote nucleation. Increasing Sr additions depressed the eutectic nucleation temperature. This may be a result of the formation of a Sr phase that could consume or detrimentally affect potent AlP nucleation sites.This work is financially supported by the Higher Education Commission of Pakistan and managerially supported from the OAD

Control of particle size in the self-assembly of amphiphilic statistical copolymers

A range of amphiphilic statistical copolymers is synthesized where the hydrophilic component is either methacrylic acid (MAA) or 2-(dimethylamino)ethyl methacrylate (DMAEMA) and the hydrophobic component comprises methyl, ethyl, butyl, hexyl, or 2-ethylhexyl methacrylate, which provide a broad range of partition coefficients (log P). Small-angle X-ray scattering studies confirm that these amphiphilic copolymers self-assemble to form well-defined spherical nanoparticles in an aqueous solution, with more hydrophobic copolymers forming larger nanoparticles. Varying the nature of the alkyl substituent also influenced self-assembly with more hydrophobic comonomers producing larger nanoparticles at a given copolymer composition. A model based on particle surface charge density (PSC model) is used to describe the relationship between copolymer composition and nanoparticle size. This model assumes that the hydrophilic monomer is preferentially located at the particle surface and provides a good fit to all of the experimental data. More specifically, a linear relationship is observed between the surface area fraction covered by the hydrophilic comonomer required to achieve stabilization and the log P value for the hydrophobic comonomer. Contrast variation small-angle neutron scattering is used to study the internal structure of these nanoparticles. This technique indicates partial phase separation within the nanoparticles, with about half of the available hydrophilic comonomer repeat units being located at the surface and hydrophobic comonomer-rich cores. This information enables a refined PSC model to be developed, which indicates the same relationship between the surface area fraction of the hydrophilic comonomer and the log P of the hydrophobic comonomer repeat units for the anionic (MAA) and cationic (DMAEMA) comonomer systems. This study demonstrates how nanoparticle size can be readily controlled and predicted using relatively ill-defined statistical copolymers, making such systems a viable attractive alternative to diblock copolymer nanoparticles for a range of industrial applications

Self-assembly of amphiphilic statistical copolymers and their aqueous rheological properties

A range of poly(n-butyl methacrylate-stat-methacrylic acid) [P(BMA-stat-MAA)] statistical copolymers of various compositions and molecular weights ranging from 5 to 30 kDa were prepared using either reversible addition-fragmentation chain transfer (RAFT) solution copolymerization or conventional free radical polymerization in isopropanol (IPA). On dilution with water, these amphiphilic copolymers self-assembled to form spherical nano-objects as confirmed by small-angle X-ray scattering (SAXS) and transmission electron microscopy. Various structural particle models were examined to extract information regarding the mean nano-object size and morphology. It is found that nano-object radii are independent of copolymer molecular weight, but depend on the copolymer composition: the smaller the amount of MAA units in the molecules the larger the nanoobjects are formed. Combined SAXS and aqueous electrophoretic measurements indicated that most of the MAA units are located at the nano-object surface. Furthermore, SAXS and rheology measurements were used to monitor the effect of solvent composition on the copolymer morphology both at a fixed copolymer concentration (either 1 wt% or 25 wt%) and also for a gradual variation in copolymer 2 concentrations (from 1 wt% to 40 wt%) when adding water to the initial copolymer solution in IPA. These studies revealed that the copolymers are present in solution as molecularly-dissolved Gaussian chains when the solvent composition is IPA-rich. However, the copolymer chains self-assemble into spherical nano-objects when the solvent composition is water-rich. At intermediate solvent compositions, SAXS analysis confirmed the formation of an interconnected nano-object network, which accounts for the apparently anomalous increase in solution viscosity on dilution indicated by rheology measurements

Childhood cognitive ability accounts for associations between cognitive ability and brain cortical thickness in old age

Associations between brain cortical tissue volume and cognitive function in old age are frequently interpreted as suggesting that preservation of cortical tissue is the foundation of successful cognitive aging. However, this association could also, in part, reflect a lifelong association between cognitive ability and cortical tissue. We analyzed data on 588 subjects from the Lothian Birth Cohort 1936 who had intelligence quotient (IQ) scores from the same cognitive test available at both 11 and 70 years of age as well as high-resolution brain magnetic resonance imaging data obtained at approximately 73 years of age. Cortical thickness was estimated at 81 924 sampling points across the cortex for each subject using an automated pipeline. Multiple regression was used to assess associations between cortical thickness and the IQ measures at 11 and 70 years. Childhood IQ accounted for more than two-third of the association between IQ at 70 years and cortical thickness measured at age 73 years. This warns against ascribing a causal interpretation to the association between cognitive ability and cortical tissue in old age based on assumptions about, and exclusive reference to, the aging process and any associated disease. Without early-life measures of cognitive ability, it would have been tempting to conclude that preservation of cortical thickness in old age is a foundation for successful cognitive aging when, instead, it is a lifelong association. This being said, results should not be construed as meaning that all studies on aging require direct measures of childhood IQ, but as suggesting that proxy measures of prior cognitive function can be useful to take into consideration

Active Galactic Nuclei at the Crossroads of Astrophysics

Over the last five decades, AGN studies have produced a number of spectacular examples of synergies and multifaceted approaches in astrophysics. The field of AGN research now spans the entire spectral range and covers more than twelve orders of magnitude in the spatial and temporal domains. The next generation of astrophysical facilities will open up new possibilities for AGN studies, especially in the areas of high-resolution and high-fidelity imaging and spectroscopy of nuclear regions in the X-ray, optical, and radio bands. These studies will address in detail a number of critical issues in AGN research such as processes in the immediate vicinity of supermassive black holes, physical conditions of broad-line and narrow-line regions, formation and evolution of accretion disks and relativistic outflows, and the connection between nuclear activity and galaxy evolution.Comment: 16 pages, 5 figures; review contribution; "Exploring the Cosmic Frontier: Astrophysical Instruments for the 21st Century", ESO Astrophysical Symposia Serie