A Polypyrrole Based Sensor for the Electrochemical Detection of OH Radicals

Polypyrrole was used as sensitive material in the development of a new device employed for the indirect detection of OH radicals. The polypyrrole film was electrosynthesized on glassy carbon. The modified electrode was exposed to the OH radicals generated by Fenton reaction. As a result of the overoxidation the conductivity of the polymer diminished very much. The overoxidation (%) was directly proportional to the ^.OH amount that reached the electrode surface. ABTS^.+, superoxide and alkylperoxy radicals did not interfere in the determination. The applicability of the device was demonstrated by estimating the ^.OH scavenging ability of ascorbic acid.     

Radial Flow in a Bounded Randomly Heterogeneous Aquifer

Flow to wells in nonuniform geologic formations is of central interest to hydrogeologists and petroleum engineers. There are, however, very few mathematical analyses of such flow. We present analytical expressions for leading statistical moments of vertically averaged hydraulic head and flux under steady-state flow to a well that pumps water from a bounded, randomly heterogeneous aquifer. Like in the widely used Thiem equation, we prescribe a constant pumping rate deterministically at the well and a constant head at a circular outer boundary of radius L. We model the natural logarithm Y = lnT of aquifer transmissivity T as a statistically homogeneous random field with a Gaussian spatial correlation function. Our solution is based on exact nonlocal moment equations for multidimensional steady state flow in bounded, randomly heterogeneous porous media. Perturbation of these nonlocal equations leads to a system of local recursive moment equations that we solve analytically to second order in the standard deviation of Y. In contrast to most stochastic analyses of flow, which require that log transmissivity be multivariate Gaussian, our solution is free of any distributional assumptions. It yields expected values of head and flux, and the variance–covariance of these quantities, as functions of distance from the well. It also yields an apparent transmissivity, T _a, defined as the negative ratio between expected flux and head gradient at any radial distance. The solution is supported by numerical Monte Carlo simulations, which demonstrate that it is applicable to strongly heterogeneous aquifers, characterized by large values of log transmissivity variance. The two-dimensional nature of our solution renders it useful for relatively thin aquifers in which vertical heterogeneity tends to be of minor concern relative to that in the horizontal plane. It also applies to thicker aquifers when information about their vertical heterogeneity is lacking, as is commonly the case when measurements of head and flow rate are done in wells that penetrate much of the aquifer thickness. Potential uses include the analysis of pumping tests and tracer test conducted in such wells, the statistical delineation of their respective capture zones, and the analysis of contaminant transport toward fully penetrating wells.     

Comparison of the C1‐symmetric diastereoisomers of a zirconocene‐based catalyst in ethylene polymerization: A benzyl substituent as a regulator in branch formation

C₁‐symmetric diastereoisomers of a zirconocene dichloride, SiMe₂(3‐benzylindenyl)(indenyl)ZrCl₂, known as catalyst precursors used to produce polypropylenes with similar molecular weights and tacticities, have been investigated in ethylene polymerization. Activated by methylaluminoxane, they produce microstructurally different polymers: high‐density polyethylene and linear low‐density polyethylene, the latter characterized by the presence of ethyl branches. The formation of branches is relevant in the complex having a sterically more crowded (inward) site. A comparison with the complex without substituents, meso‐SiMe₂(indenyl)₂ZrCl₂, shows that the presence of a benzyl group on only one of the two indenyl moieties can regulate the number of branches and the molecular weight of the macromolecule. Actually, the unsubstituted complex is able to give double the number of branches and lower molecular weights, whereas the C₁‐symmetric disubstituted complexes previously reported generally give linear polyethylene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3551–3555, 2006     

Modulation of ionization and structural properties of weak polyelectrolytes due to 1D, 2D,and 3D confinement

What is the impact of reducing the space available to molecules onto their properties is a fundamental question for capillary systems, molecular biology and transport, protein and material sciences. Possibly influenced by space restriction, ionization degree has rarely been studied for confined polyelectrolytes; Monte Carlo titrations and coarse‐grained models are thus used to investigate structural and ionization changes induced on a single polyelectrolyte chain by confinement into slit (1D), cylindrical (2D), or spherical (3D) cavities. Four polyelectrolyte models differing in chain stiffness and the possible formation of charged hydrogen bonds (c? H? bonds) are studied. Low pH effective ionization constants (pK_a ) of confined chains are lower than for the free species if c? H? bonds can be formed. This is especially evident for 3D‐confined stiff chains, a finding rationalized by the impact of global compression onto chain conformations. If no c? H? bonds are allowed, chain ionization is largely unaffected by 1D or 2D confinement, while it is depressed by 3D. Chain confinement Helmholtz energy (ΔA _conf) was computed as a function of both pH and confining width (W) to gauge the impact of ionization‐induced stiffening onto ΔA _conf versus W behavior, the partition coefficient governing absorption, and the average number of c? H? bond formed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1088–1102     

(Liquid + liquid) equilibria in {water + acrylic acid + (1-butanol,or 2-butanol,or 1-pentanol)} systems at T = 293.2 K,T = 303.2 K,and T = 313.2 K and atmospheric pressure

(Liquid + liquid) equilibrium (LLE) data for {water + acrylic acid + (1-butanol, or 2-butanol, or 1-pentanol)} at T = 293.2 K, T = 303.2 K, and T = 313.2 K and atmospheric pressure (≈95 kPa) were determined by Karl Fischer titration and densimetry. All systems present type I binodal curves. The size of immiscibility region changes little with an increase in temperature, but increases according to the solvent, following the order: 2-butanol < 1-butanol < 1-pentanol. Values of solute distribution and solvent selectivities show that 1-pentanol is a better solvent than 1-butanol or 2-butanol for acrylic acid removal from water solutions. Quality of data was ascertain by Hand and Othmer-Tobias equations, giving R² > 0.916, mass balance and accordance between tie lines and cloud points. The NRTL model was used to correlate experimental data, by estimating new energy parameters, with root mean square deviations below 0.0053 for all systems.     

Effect of Molecular Architecture on Physical Properties of Tree-Shaped and Star-Shaped Poly(Methyl Methacrylate)-Based Copolymers

The synthesis of star-like A(B)_n copolymers based on the hydrophilic poly(ethylene glycol) monomethyl ether (m-PEG, block A) and the hydrophobic poly(methyl methacrylate) (PMMA, blocks B) is reported. We obtained copolymers made of one m-PEG chain and 2 or 4 PMMA blocks using a combined “arm first”—“core first” approach. Such structures were called tree-shaped copolymers where the m-PEG was considered as the trunk and PMMA arms as the branches. Star-like copolymers (B)_nA-A(B)_n built by two tree-shaped fragments with a poly(propylene oxide) (PPO) as the central junction, were also synthesized according to a previously reported procedure. The latter were called star-shaped structures and the synthesis was performed to obtain architectures different from the tree-shaped one but characterized by a similar length of the PMMA arms. Microstructural analysis was carried out through ¹H-NMR and GPC, and the thermal and transport properties (sorption and diffusion) to liquid water were investigated and correlated to the molecular architecture of the two classes of copolymers.     

On the experimental determination of some mechanical properties of porcine periodontal ligament

This work analyzes some aspects of the experimental determination of the mechanical properties of the periodontal ligament (PDL). The necessity of extracting small samples, with a geometry as regular as possible, from a complex biological structure, makes it quite difficult both to establish a correct testing protocol and to obtain reliable results, for instance usable by bioengineers to develop constitutive models. Here, by means of more than 250 experiments performed on small samples of porcine PDL, we try both to provide some statistically significant information, and to clarify some issues related to the testing protocols. Some basic mechanical parameters for the PDL (Young’s modulus, shear modulus, failure stress and strain for tension, compression, and shear tests) are measured, and a relevant statistical analysis is provided. The influence of some experimental parameters (sample conservation procedure, testing modalities), is also studied; on the basis of our results, we can conclude that (i) if conservation is needed, a cooling at −80° is sufficient to guarantee statistically significant results, (ii) it is important to perform at least the compression tests keeping the samples immersed in pressurized fluid, and (iii) preconditioning cycles are necessary only for studying the initial (toe) region of the stress–strain curves. It is also observed that, with these types of samples, some special care is required when computing stresses and strains from force and displacement measurements. In order to illustrate this aspect, some non-linear Finite Element analyses are performed, aimed at evaluating the influence of the sample geometry on the stress and strain calculation. Finally, the issue of fiber damage due to the cutting procedures is briefly discussed.     

Localization of Mean Flow and Apparent Transmissivity Tensor for Bounded Randomly Heterogeneous Aquifers

We explore the concept of apparent transmissivity for bounded randomly heterogeneous media under steady-state flow regime. The novelty of our study consists of investigating a tensorial nature of apparent transmissivity. We demonstrate that apparent transmissivity of bounded domains is anisotropic even though an underlying local transmissivity field is statistically isotropic. For rectangular flow domains, we derive an analytical expression for the apparent transmissivity tensor via localization and perturbation expansion of the nonlocal mean flow equations in the variance of log-transmissivity. In this expression, almost everywhere the off-diagonal terms are several orders of magnitude smaller than the diagonal terms. When the domain size relative to the log-transmissivity correlation scale is large, the longitudinal and transverse components of the apparent transmissivity tensor approach the geometric mean of local transmissivity. While rigorously valid for mean uniform flows only, our expression for the apparent transmissivity tensor leads to mean hydraulic head distributions that compare favorably with those obtained through Monte-Carlo simulations and the nonlocal mean flow equations even in the presence of pumping wells. This agreement deteriorates in the vicinity of wells and as pumping rates increase.     

Composite quarks and cabibbo mixing

We suggest that certain discrete chiral symmetries, which are remnants of axial U(1) symmetries of a more fundamental theory, may explain the origin of the relation, tan θ_c ≈- √m_d/m_s. Simple models illustrating this idea are constructed in which quarks and standard techniquarks appear as composite states made of a more fundamental set of fermions.