Dynamical Monte Carlo Study of Equilibrium Polymers : Static Properties

We report results of extensive Dynamical Monte Carlo investigations on self-assembled Equilibrium Polymers (EP) without loops in good solvent. (This is thought to provide a good model of giant surfactant micelles.) Using a novel algorithm we are able to describe efficiently both static and dynamic properties of systems in which the mean chain length \Lav is effectively comparable to that of laboratory experiments (up to 5000 monomers, even at high polymer densities). We sample up to scission energies of $E/k_BT=15$ over nearly three orders of magnitude in monomer density $\phi$, and present a detailed crossover study ranging from swollen EP chains in the dilute regime up to dense molten systems. Confirming recent theoretical predictions, the mean-chain length is found to scale as \Lav \propto \phi^\alpha \exp(\delta E) where the exponents approach $\alpha_d=\delta_d=1/(1+\gamma) \approx 0.46$ and $\alpha_s = 1/2 [1+(\gamma-1)/(\nu d -1)] \approx 0.6, \delta_s=1/2$ in the dilute and semidilute limits respectively. The chain length distribution is qualitatively well described in the dilute limit by the Schulz-Zimm distribution \cN(s)\approx s^{\gamma-1} \exp(-s) where the scaling variable is s=\gamma L/\Lav. The very large size of these simulations allows also an accurate determination of the self-avoiding walk susceptibility exponent $\gamma \approx 1.165 \pm 0.01$. ....... Finite-size effects are discussed in detail.Comment: 15 pages, 14 figures, LATE

Gaussians versus back-to-back exponentials: a numerical study

The underlying magnetic field distribution in many samples studied by the mu R technique is asymmetric. Despite this, quite often fit functions assuming symmetric (Gaussian) distributions are used. Here, a back-to-back exponential function, which can be made asymmetric with fit parameters, is studied numerically alongside a Gaussian function to see how well each fits symmetric and asymmetric simulated data. Both fit symmetric data well, but the back-to-back exponential is found to be superior for fitting asymmetric data

Kinetic Control in the Regioselective Alkylation of Pterin Sensitizers: A Synthetic, Photochemical, and Theoretical Study

Alkylation patterns and excited-state properties of pterins were examined both experimentally and theoretically. 2D NMR spectroscopy was used to characterize the pterin derivatives, revealing undoubtedly that the decyl chains were coupled to either the O4 or N3 sites on the pterin. At a temperature of 70°C, the pterin alkylation regioselectively favored the O4 over the N3. The O4 was also favored when using solvents, in which the reactants had increased solubility, namely N,N-dimethylformamide and N,N-dimethylacetamide, rather than solvents in which the reactants had very low solubility (tetrahydrofuran and dichloromethane). Density functional theory (DFT) computed enthalpies correlate to regioselectivity being kinetically driven because the less stable O-isomer forms in higher yield than the more stable N-isomer. Once formed these compounds did not interconvert thermally or undergo a unimolecular ?walk? rearrangement. Mechanistic rationale for the factors underlying the regioselective alkylation of pterins is suggested, where kinetic rather than thermodynamic factors are key in the higher yield of the O-isomer. Computations also predicted greater solubility and reduced triplet state energetics thereby improving the properties of the alkylated pterins as 1 O 2 sensitizers. Insight on thermal and photostability of the alkylated pterins is also provided.Fil: Walalawela, Niluksha. City University of New York; Estados UnidosFil: Vignoni, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. City University of New York; Estados UnidosFil: Urrutia, María Noel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Belh, Sarah J.. City University of New York; Estados UnidosFil: Greer, Edyta M.. City University of New York; Estados UnidosFil: Thomas, Andrés Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Greer, Alexander. City University of New York; Estados Unido

Identification And Characterization Of A Second Encephalitogenic Determinant Of Myelin Proteolipid Protein (Residues 178-191) For SJL Mice

We previously described a synthetic peptide of myelin proteolipid protein (PLP), peptide 139-151, which induces experimental allergic encephalomyelitis in SJL/J (H-2s) mice. We have now identified an additional determinant, PLP residues 178-191, that is also a potent encephalitogen in this strain. When PLP peptide 178-191 was compared with peptide 139-151 on an equimolar basis, the day of onset of disease induced by PLP 178-191 was earlier, but the incidence, severity, and histologic features were indistinguishable. Lymph node cells from animals immunized with the whole PLP molecule responded to both PLP 178-191 and 139-151, suggesting immunologic codominance of the two epitopes. PLP 178-191 elicited stronger proliferative responses and this may relate to the earlier onset of disease induced with this peptide. Two CD4+, peptide-specific, I-A(s)-restricted T cell lines, selected by stimulation of lymph node cells with either PLP 178-191 or 139-151, were each encephalitogenic in naive syngeneic mice. The presence of multiple encephalitogenic codominant PLP epitopes within a single mouse strain emphasizes the complexity of the immune response to PLP and its potential as a target Ag in autoimmune demyelinating diseases

Slip statistics of dislocation avalanches under different loading modes

Slowly compressed microcrystals deform via intermittent slip events, observed as displacement jumps or stress drops. Experiments often use one of two loading modes: an increasing applied stress (stress driven, soft), or a constant strain rate (strain driven, hard). In this work we experimentally test the influence of the deformation loading conditions on the scaling behavior of slip events. It is found that these common deformation modes strongly affect time series properties, but not the scaling behavior of the slip statistics when analyzed with a mean-field model. With increasing plastic strain, the slip events are found to be smaller and more frequent when strain driven, and the slip-size distributions obtained for both drives collapse onto the same scaling function with the same exponents. The experimental results agree with the predictions of the used mean-field model, linking the slip behavior under different loading modes

Application of a Self-Similar Pressure Profile to Sunyaev-Zel'dovich Effect Data from Galaxy Clusters

We investigate the utility of a new, self-similar pressure profile for fitting Sunyaev-Zel'dovich (SZ) effect observations of galaxy clusters. Current SZ imaging instruments - such as the Sunyaev-Zel'dovich Array (SZA) - are capable of probing clusters over a large range in physical scale. A model is therefore required that can accurately describe a cluster's pressure profile over a broad range of radii, from the core of the cluster out to a significant fraction of the virial radius. In the analysis presented here, we fit a radial pressure profile derived from simulations and detailed X-ray analysis of relaxed clusters to SZA observations of three clusters with exceptionally high quality X-ray data: A1835, A1914, and CL J1226.9+3332. From the joint analysis of the SZ and X-ray data, we derive physical properties such as gas mass, total mass, gas fraction and the intrinsic, integrated Compton y-parameter. We find that parameters derived from the joint fit to the SZ and X-ray data agree well with a detailed, independent X-ray-only analysis of the same clusters. In particular, we find that, when combined with X-ray imaging data, this new pressure profile yields an independent electron radial temperature profile that is in good agreement with spectroscopic X-ray measurements.Comment: 28 pages, 6 figures, accepted by ApJ for publication (probably April 2009

The Ultrasensitivity of Living Polymers

Synthetic and biological living polymers are self-assembling chains whose chain length distributions (CLDs) are dynamic. We show these dynamics are ultrasensitive: even a small perturbation (e.g. temperature jump) non-linearly distorts the CLD, eliminating or massively augmenting short chains. The origin is fast relaxation of mass variables (mean chain length, monomer concentration) which perturbs CLD shape variables before these can relax via slow chain growth rate fluctuations. Viscosity relaxation predictions agree with experiments on the best-studied synthetic system, alpha-methylstyrene.Comment: 4 pages, submitted to Phys. Rev. Let

The Role of Social Support in Predicting Depression and Task Overload Among College Students

Guided by the Relationships Motivation Theory, this short-term longitudinal study examined associations between social support (i.e., relatedness), depression, and stress in the form of task overload among emerging adult, university students (N = 184 at time one; N = 105 at time two; 69.2% female). Results from a series of path models indicated a significant relationship between decreased perceptions of social support over time and an increase in perceived task overload with significant mediating effects through depressive symptomology. Implications for counseling services as well as intervention and awareness points for university professionals are discussed