Film Formation from Nanosized Copolymeric Latex Particles: A Photon Transmission Study

The photon transmission technique was used to monitor the evolution of transparency during film formation from nanosized copolymeric latex particles. The latex films were prepared from poly(methyl methacrylate-co-butyl methacrylate) (P(MMA-co-BMA)) particles which were produced by microemulsion polymerization. These films were annealed at elevated temperatures in various time intervals above the glass transition temperature (T(g)) of P(MMA-co-BMA). It is observed that the transmitted photon intensity (I(tr)) from these films increased as the annealing temperature increased. There are three different film formation stages. These stages are explained by the void closure, healing, and interdiffusion processes, respectively. The activation energies for viscous flow (DeltaH approximately 16 kcal/mol), minor chains (DeltaE(H) approximately 27 kcal/mol), and backbone motion (Delta E(b) approximately 132 kcal/mol) were obtained using various models. Void closure (tau(v), T(v)) and healing points (tau(H), T(H)) were determined. Using the time-temperature pairs, void closure and healing activation energies were measured and found to be 21 and 30 kcal/mol, respectively. Copyright 2001 Academic Press.     

Development of a solid‐phase microextraction LC–MS/MS method for determination of oxidative stress biomarkers in biofluids

Recently the connection between oxidative stress and various diseases, including cancer and Alzheimer's, attracts notice as a pathway suitable for diagnostic purposes. 8‐Oxo‐deoxyguanosine and 8‐oxo‐deoxyadenosine produced from the interaction of reactive oxygen species with DNA become prominent as biomarkers. Several methods have been developed for their determination in biofluids, including solid‐phase extraction and enzyme‐linked immunosorbent assays. However, still, there is a need for reliable and fast analytical methods. In this context, solid‐phase microextraction offers many advantages such as flexibility in geometry and applicable sample volume, as well as high adaptability to high‐throughput sampling. In this study, a solid‐phase microextraction method was developed for the determination of 8‐oxo‐deoxyguanosine and 8‐oxo‐deoxyadenosine in biofluids. The extractive phase of solid‐phase microextraction consisted of hydrophilic–lipophilic balanced polymeric particles. In order to develop a solid‐phase microextraction method suitable for the determination of the analytes in saliva and urine, several parameters, including desorption solvent, desorption time, sample pH, and ionic strength, were scrutinized. Analytical figures of merit indicated that the developed method provides reasonable interday and intraday precisions (<15% in both biofluids) with acceptable accuracy. The method provides a limit of quantification for both biomarkers at 5.0 and 10.0 ng/mL levels in saliva and urine matrices, respectively.     

Water‐Soluble Metallocene‐Containing Polymers

Metallocenes are organometallic compounds with reversible redox profiles and tunable oxidation and reduction potentials, depending on the metal and substituents at the cyclopentadienyl rings. Metallocenes have been introduced in macromolecules to combine the redox‐activity with polymer properties. There are many examples of such hydrophobic polymer materials, but much fewer water‐soluble examples are found scattered across the polymer literature. However, in terms of drug delivery and other biological applications, water solubility is essential. For this very reason, all the synthetic routes to water‐soluble metallocene containing polymers are collected and discussed here. The focus is on neutral ferrocene‐ and ruthenocene‐containing and charged cobaltocenium‐containing macromolecules (i.e., symmetrical sandwich complexes). The synthetic protocols, self‐assembly behavior, and other benefits of the obtained materials are discussed.

     

Approximate Analytical Solutions of the Dirac Equation for Yukawa Potential Plus Tensor Interaction with Any κ-Value

Approximate analytical solutions of the Dirac equation are obtained for the Yukawa potential plus a tensor interaction with any κ-value for the cases having the Dirac equation pseudospin and spin symmetry. The potential describing tensor interaction has a Yukawa-like form. Closed forms of the energy eigenvalue equations and the spinor wave functions are computed by using the Nikiforov–Uvarov method. It is observed that the energy eigenvalue equations are consistent with the ones obtained before. Our numerical results are also listed to see the effect of the tensor interaction on the bound states.     

X‐ray diffraction analysis of powder and thin film of (Gd1‐x Yx)2O3 prepared by sol‐gel process

The mixed oxide (Gd_1‐xY_x)₂O₃ (0.0 ≤ x ≤ 1.0) were synthesized, as powder and thin film, by a sol‐gel process. X‐ray diffraction data were collected and crystal structure and microstructure analysis were performed using Rietveld refinement method. All samples were found to have the same crystal system and formed solid solutions over the whole range of x. The cationic distribution, Gd³⁺ and Y³⁺, over the two non‐equivalent sites 8b and 24d of the space group Ia3 is found to be random for all values of (x). The lattice parameter is found to vary linearly with the composition (x). Replacing Gd³⁺ and Y³⁺ by each other introduces a systemic decrease in the x‐coordinate of cation position (24d) and slight changes in the oxygen coordinates. Crystallite size and microstrain analysis is performed along different crystallographic directions and anisotropic changes are found with the composition parameter (x). The average crystallite size ranges from 75 to 149 nm and the r.m.s strain from 0.027 to 0.068 x10^‐2. Textured Gd_1.841Y_0.159O₃ (400) buffer layers, with a high degree of alignment in both out‐plane and in‐plan, are successfully grown on cube textured Ni (001) tape substrates by sol–gel dip coating process. The resulting buffer layers are crack‐free, pinhole‐free, dense and smooth. YbBa₂Cu₃O_7‐x (YbBCO) thin film could be (00l) epitaxially grown on the obtained buffer layer using sol–gel dipping technique. (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

PEG–Anthracene Hydrogels as an On‐Demand Stiffening Matrix To Study Mechanobiology

There is a growing interest in materials that can dynamically change their properties in the presence of cells to study mechanobiology. Herein, we exploit the 365 nm light mediated [4+4] photodimerization of anthracene groups to develop cytocompatible PEG‐based hydrogels with tailorable initial moduli that can be further stiffened. A hydrogel formulation that can stiffen from 10 to 50 kPa, corresponding to the stiffness of a healthy and fibrotic heart, respectively, was prepared. This system was used to monitor the stiffness‐dependent localization of NFAT, a downstream target of intracellular calcium signaling using a reporter in live cardiac fibroblasts (CFbs). NFAT translocates to the nucleus of CFbs on stiffening hydrogels within 6 h, whereas it remains cytoplasmic when the CFbs are cultured on either 10 or 50 kPa static hydrogels. This finding demonstrates how dynamic changes in the mechanical properties of a material can reveal the kinetics of mechanoresponsive cell signaling pathways that may otherwise be missed in cells cultured on static substrates.     

Vapor-induced film formation from low-Tg particles for different solvent compositions

The photon transmission method was used to study latex film formation from poly(vinyl acetate) (PVAc) particles induced by two different solvents. Films with the same latex content were prepared from PVAc particles and exposed to vapor of ethanol-water and acetone-water mixtures in various compositions. Transmitted photon intensities, Itr, from these films increased with increasing vapor exposure time. The increase in Itr is attributed to the increase in crossing density at the polymer-polymer junction. The Prager-Tirrell model was employed to obtain the back-and-forth frequency, nu, of the reptating polymer chain during film formation induced by solvent vapor. It was observed that the produced nu values increase as the solvent content is increased for both solvents. Abilities of both solvents to form films were interpreted with the solubility parameters of the solvents and the PVAc.