Kinetics of cotelomerization of 3-(trimethoxysilyl)propyl methacrylate and perfluorodecylacrylate

The telomerization of 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) in the presence of 2-mercaptoethanol was investigated at 80 °C in acetonitrile. In our case, the efficiency of 2-mercaptoethanol as telogen agent, with TMSPMA, was demonstrated and the transfer constant (C_T) was determined. Moreover, cotelomerization of TMSPMA with perfluorodecylacrylate (PFDA) using various PFDA contents was investigated in order to obtain α-hydroxy oligomers with statistical copolymer-type main chains bearing trimethoxysilyl and perfluoro pendant chains. Until 10 mol% PFDA, no phase separation occured. In this composition, r_TMSPMA and r_PFDA reactivity ratios were calculated, thus showing a tendency for a statistical distribution of the monomer units in the copolymer.     

Large Deviations Analysis for Distributed Algorithms in an Ergodic Markovian Environment

We provide a large deviations analysis of deadlock phenomena occurring in distributed systems sharing common resources. In our model transition probabilities of resource allocation and deallocation are time and space dependent. The process is driven by an ergodic Markov chain and is reflected on the boundary of the d-dimensional cube. In the large resource limit, we prove Freidlin-Wentzell estimates, we study the asymptotic of the deadlock time and we show that the quasi-potential is a viscosity solution of a Hamilton-Jacobi equation with a Neumann boundary condition. We give a complete analysis of the colliding 2-stacks problem and show an example where the system has a stable attractor which is a limit cycle.     

Multiscale Modeling of Branch Length in Butyl Acrylate Solution Polymerization

Branch lengths resulting from both backbiting and intermolecular chain transfer to polymer are examined for the solution polymerization of butyl acrylate, using a rate‐equation model and ordinary differential equations. Backbiting is allowed to generate branches of varying length, according to a cumulative distribution function obtained from a lattice kinetic Monte Carlo simulation. About 8% of the branches produced by backbiting are 10 mers or longer. In contrast to common assumptions about the origins of short‐chain and long‐chain branches, the model indicates that nearly all of the long‐chain branches may be produced by backbiting, rather than intermolecular chain transfer to polymer.

     

Model calculations of the particle spectrum of the galactic cosmic ray (GCR) environment: Assessment with ACE/CRIS and MARIE measurements

For a given galactic cosmic ray (GCR) environment, understanding the distribution of the particle flux (protons, alpha particles, and heavy ions) in deep-space and on the surface of planetary systems such as Mars are essential for the risk assessment of future human exploration missions. In our model calculations, we make use of the NASA's HZETRN (High Z and Energy Transport) code along with the nuclear fragmentation cross sections that are described by the quantum multiple scattering (QMSFRG) model with the time-dependant variation of the GCR environment derived making use of the solar modulation potential, phi. Data from the cosmic ray isotope spectrometer (CRIS) instrument onboard the advanced composition explorer (ACE) has been available from 1998. Data from the CRIS instrument is being analyzed to understand the short term variations in the particle spectrum during the current solar cycle phase. In this report, particle spectrum for December 2002 of the CRIS instrument was compared with the model calculations. Current assessment of the model calculations show very good agreement of the particle flux (15% for low Z and 5% for high Z) data from Boron (Z=5) through Nickel (Z=28) nuclei for the energy bins reported by CRIS. Similarly, the model calculated dose–rate calculations are compared with the proton flux measured dose–rate from the Martian Radiation Environment Experiment (MARIE) currently onboard the 2001 Mars Odyssey spacecraft in Martian orbit for the month of August 2003 that is representative of a quiet-time GCR data at Mars. Current model calculations are well within 10% of the measured observations of MARIE. The predictive capabilities of the quiet-time GCR particle flux model calculations are promising for biological and shielding studies and for the radiation risk assessment for future human explorations.     

Time-dependent Delta-interactions for 1D Schrödinger Hamiltonians

The non autonomous Cauchy problem \(i\partial_{t}u=-\partial_{xx}^{2} u+\alpha(t) \delta_{0}u\) with u _t?=?0?=?u ₀ is considered in L ² (?) . The regularity assumptions for α are accurately analyzed and show that the general results for non autonomous linear evolution equations in Banach spaces are far from being optimal. In the mean time, this article shows an unexpected application of paraproduct techniques, initiated by J.M. Bony for nonlinear partial differential equations, to a classical linear problem.     

Sequential,Ultrafast Energy Transfer and Electron Transfer in a Fused Zinc Phthalocyanine-free-base Porphyrin-C60 Supramolecular Triad

A supramolecular triad composed of a fused zinc phthalocyanine-free-base porphyrin dyad (ZnPc-H₂P) coordinated to phenylimidazole functionalized C₆₀ via metal-ligand axial coordination was assembled, as a photosynthetic antenna-reaction centre mimic. The process of self-assembly resulting into the formation of C₆₀Im:ZnPc-H₂P supramolecular triad was probed by proton NMR, UV-Visible and fluorescence experiments at ambient temperature. The geometry and electronic structures were deduced from DFT calculations performed at the B3LYP/6-31G(dp) level. Electrochemical studies revealed ZnPc to be a better electron donor compared to H₂P, and C₆₀ to be the terminal electron acceptor. Fluorescence studies of the ZnPc-H₂P dyad revealed excitation energy transfer from ¹H₂P* to ZnPc within the fused dyad and was confirmed by femtosecond transient absorption studies. Similar to that reported earlier for the fused ZnPc-ZnP dyad, the energy transfer rate constant, k_ENT was in the order of 10¹² s⁻¹ in the ZnPc-H₂P dyad indicating an efficient process as a consequence of direct fusion of the two π-systems. In the presence of C₆₀Im bound to ZnPc, photoinduced electron transfer leading to H₂P-ZnPc^.+:ImC₆₀^.− charge separated state was observed either by selective excitation of ZnPc or H₂P. The latter excitation involved an energy transfer followed by electron transfer mechanism. Nanosecond transient absorption studies revealed that the lifetime of charge separated state persists for about 120 ns indicating charge stabilization in the triad.     

Excited‐State Charge Transfer in Covalently Functionalized MoS2 with a Zinc Phthalocyanine Donor–Acceptor Hybrid

The functionalization of MoS₂ is of paramount importance for tailoring its properties towards optoelectronic applications and unlocking its full potential. Zinc phthalocyanine (ZnPc) carrying an 1,2‐dithiolane oxide linker was used to functionalize MoS₂ at defect sites located at the edges. The structure of ZnPc‐MoS₂ was fully assessed by complementary spectroscopic, thermal, and microscopy imaging techniques. An energy‐level diagram visualizing different photochemical events in ZnPc‐MoS₂ was established and revealed a bidirectional electron transfer leading to a charge separated state ZnPc^{. +} ‐MoS₂^.?. Markedly, evidence of the charge transfer in the hybrid material was demonstrated using fluorescence spectroelectrochemistry. Systematic studies performed by femtosecond transient absorption revealed the involvement of excitons generated in MoS₂ in promoting the charge transfer, while the transfer was also possible when ZnPc was excited, signifying their potential in light‐energy‐harvesting devices.     

An easy sol–gel route for deposition of oriented Ln2Ti2O7 (Ln=La,Nd) films on SrTiO3 substrates

The effect of the orientation of SrTiO₃ (STO) substrates, (1 0 0) or (1 1 0), on the growth of La₂Ti₂O₇ (LTO) and Nd₂Ti₂O₇ (NTO) thin films was investigated. The films were deposited via a sol–gel process coupled to the spin-coating technique. Depending on the substrate orientation, a similar effect was observed on the structural properties for both the LTO and NTO thin films. For (1 1 0)-oriented STO substrate, the films are preferentially (0 0 1) oriented while for (1 0 0)-oriented STO substrates, the orientation is mainly (0 1 2). Those matching appear to be in good agreement with the compatibility between the film/substrate crystal lattices, in relation with the existence of perovskite slabs in Ln₂Ti₂O₇ (Ln=rare earth) compounds. In these latter, a slight disorientation of the (0 1 2) planes with respect to the surface of the substrate was measured. This tilting is even more marked in the case of NTO. The surface morphology was studied by atomic force microscopy.     

Goal Directedness,Chemical Organizations,and Cybernetic Mechanisms

In this article, we attempt at developing a scenario for the self-organization of goal-directed systems out of networks of (chemical) reactions. Related scenarios have been proposed to explain the origin of life starting from autocatalytic sets, but these sets tend to be too unstable and dependent on their environment to maintain. We apply instead a framework called Chemical Organization Theory (COT), which shows mathematically under which conditions reaction networks are able to form self-maintaining, autopoietic organizations. We introduce the concepts of perturbation, action, and goal based on an operationalization of the notion of change developed within COT. Next, we incorporate the latter with notions native to the theory of cybernetics aimed to explain goal directedness: reference levels and negative feedback among others. To test and refine these theoretical results, we present some examples that illustrate our approach. We finally discuss how this could result in a realistic, step-by-step scenario for the evolution of goal directedness, thus providing a theoretical solution to the age-old question of the origins of purpose.     

PIV Measurements in the Near and Intermediate Field Regions of Jets Issuing from Eight Different Nozzle Geometries

An experimental study was conducted to investigate the effect of nozzle geometry on the mixing characteristics and turbulent transport phenomena in turbulent jets. The nozzle geometry examined were round, square, cross, eight-corner star, six-lobe daisy, equilateral triangle as well as ellipse and rectangle each with aspect ratio of 2. The jets were produced from sharp linear contoured nozzles which may be considered intermediate to the more widely studied smooth contraction and orifice nozzles. A high resolution particle image velocimetry was used to conduct detailed velocity measurements in the near and intermediate regions. It was observed that the lengths of the potential cores and the growth rates of turbulence intensities on the jet centerline are comparable with those of the orifice jets. The results indicate that the decay and spreading rates are lower than reported for orifice jets but higher than results for smooth contoured jets. The jets issuing from the elliptic and rectangular nozzles have the best mixing performance while the least effective mixing was observed in the star jet. The distributions of the Reynolds stresses and turbulent diffusion clearly showed that turbulent transport phenomena are quite sensitive to nozzle geometry. Due to the specific shape of triangular and daisy jets, the profiles of mean velocity and turbulent quantities are close to each other in their minor and major planes while in the elliptic and rectangular jets are considerably different. They also exhibit more isotropic behavior compared to the elliptic and rectangular jets. In spite of significant effects of nozzle geometry on mean velocity and turbulent quantities, the integral length scales are independent of changes in nozzle geometry.