Structure–properties investigations in hydrophilic nanocomposites based on polyurethane/poly(2–hydroxyethyl methacrylate) semi‐interpenetrating polymer networks and nanofiller densil for biomedical application

Nanocomposites based on sequential semi–interpenetrating polymer networks (semi–IPNs) of crosslinked polyurethane and linear poly(2‐hydroxyethyl methacrylate) filled with 1–15 wt % of nanofiller densil were prepared and investigated. Nanofiller densil used in an attempt to control the microphase separation of the polymer matrix by polymer–filler interactions. The morphology (SAXS, AFM), mechanical properties (stress–strain), thermal transitions (DSC) and polymer dynamics (DRS, TSDC) of the nanocomposites were investigated. Special attention has been paid to the raising of the hydration properties and the dynamics of water molecules in the nanocomposites in the perspective of biomedical applications. Nanoparticles were found to aggregate partially for higher than 3 and 5 wt % filler loading in semi–IPNs with 17 and 37 wt % PHEMA, respectively. The results show that the good hydration properties of the semi–IPN matrix are preserved in the nanocomposites, which in combination with results of thermal and dielectric techniques revealed also the existence of polymer–polymer and polymer–filler interactions. These interactions results also in the improvement of physical and mechanical properties of the nanocomposites in compare with the neat matrix. The improvement of mechanical properties in combination with hydrophilicity and biocompatibility of nanocomposites are promising for use these materials for biomedical application namely as surgical films for wound treatment and as material for producing the medical devises. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43122.     

The Effect of La2O3 Addition on Sol–Gel Derived Mullitization

Monophasic gel with stoichiometric 3Al₂O₃·2SiO₂ composition and gels with 0.99, 1.96, and 2.91 mol% La₂O₃ added were sol–gel derived. The crystallization path, structure evolution, microstructure, and morphology of calcined premullite powders and sintered ceramic bodies have been investigated as a function of La₂O₃ content and sintering temperature. In addition to mullite, spinel phase at about 980°C, and α‐alumina at above 1000°C were determined; however, neither La₂O₃ nor La‐related compounds had crystallized. The La₂O₃ predominately incorporated into the glassy phase, enhanced with La₂O₃ level, which affected both mullite structure and composition, as confirmed by electron microscopy, Rietveld structure refinement, determination of unit cell parameters, electron microscopy, and achieved density of the sintered bodies. Increased thermal treatment changes the alumina/silica ratio in mullite (towards 3:2 below 1200°C, and toward 2:1 above), and decreases the mullite/amorphous ratio. Sintered dense ceramic bodies revealed a positive densification effect and increased sinterability as a result of the lanthanum‐induced increase in glassy phase.     

Preparation of polymeric nanocapsules via nano-sized poly(methoxydiethyleneglycol methacrylate) colloidal templates

Polymeric nanocapsules are attractive devices with a number of potential applications. In the present contribution we describe a method for nanocapsule preparation which is based on the formation of nanosized templates (mesoglobules, prepared from thermo-responsive poly(methoxydiethyleneglycol methacrylate)s, PDEGMA). These mesoglobules were coated with a cross-linked shell formed by pseudo-seeded radical polymerization of either N-isopropylacrylamide or 2-hydroxyethylmethacrylate in the presence of a cross-linking agent. Dissolution and removal of templates were achieved by extensive dialysis against water at temperatures below the LCST of PDEGMA. The obtained nanocapsules were visualized by transmission electron microscopy and their dimensions were determined by dynamic light scattering. The differences in the morphology of the nanocapsules were attributed to the different structures of the cross-linked membranes.     

Material properties and fire test results

Five material properties commonly used to describe the fire behavior of solids were evaluated as sole explanatory variables for four small‐scale fire tests with pass/fail outcomes by using a physically based probabilistic (phlogistic) burning model. The phlogistic model describes the likelihood of passing vertical Bunsen burner tests and a regulatory heat release rate test reasonably well over a wide range of material properties, as deduced from the correlation coefficient and mean deviation of the predicted and measured values. Of the thermal, combustion, and fire properties examined, the best predictors of the likelihood of passing the fire tests of this study were the heat of combustion of the sample, the heat release capacity, and the heat release parameter. The relative merits and drawbacks of qualitative (threshold) and quantitative (probabilistic) approaches to predicting fire test results using thermal and combustion properties are discussed. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

Actor networks and the construction of applicable knowledge: the case of the Timbre Brownfield Prioritization Tool

This article deals with experiences acquired during the process of developing the Timbre Brownfield Prioritization Tool (TBPT). Developing a decision support tool that takes into account the expectations and experiences of its potential users is similar to creating applicable knowledge by the joint action of scientists and heterogeneous actors. Actor network theory is used to explore the construction of this form of applicable knowledge as a process of actor network creation. Following the French sociologist Callon, networks are seen to be initiated and carried out by a group of scientists (tool developers) via four moments of translation, called problematization, interessement, enrolment and mobilization. Each step in the construction of the TBPT—from the initial research question to the final model—can be linked in retrospect to changing configurations of actor networks. Based on the experiences of the tool developers in the Czech Republic, Poland, Germany and Romania, we illustrate how these configurations varied across space and time. This contribution emphasizes the ability to correlate gains in knowledge with the more visible changes in the scope of actor networks in order to highlight achievements but also limitations in acquiring applicable knowledge.     

Formation of mesoglobules in aqueous media from thermo-sensitive poly(ethoxytriethyleneglycol acrylate)

A series of six poly(ethoxytriethyleneglycol acrylate) (PETEGA) homopolymers were synthesized by atom transfer radical polymerization, reversible addition-fragmentation transfer polymerization, and anionic polymerization in order to cover a molecular weight range from 7,000 to 40,000 Da. The polymers exhibited a lower critical solution temperature (LCST) behavior in water, which was observed by the occurrence of a cloud point (CP) at around 35 °C. The transmittance of visible light versus temperature dependence overlapped during the cooling and the heating cycles, showing almost a complete lack of hysteresis. Moreover, instead of the occurrence of an uncontrolled macroscopic phase separation, stable colloidal aggregates (mesoglobules) of narrow distribution in particle size were formed in water at temperatures above the LCST of PETEGA at 1 g L⁻¹ solutions. The dimensions of the mesoglobules ranged from 91 to 235 nm, and particle size was not influenced by the molecular weight of PETEGA. Temperature changes caused considerable variations of the mesoglobules dimensions, which were smaller at higher temperatures. The addition of an anionic surfactant simultaneously increased the CP values by 4–6 °C and lowered the dimensions of the mesoglobules.     

Fourier Analysis of Serial Dependence Measures

Classical spectral analysis is based on the discrete Fourier transform of the autocovariances. In this article we investigate the asymptotic properties of new frequency‐domain methods where the autocovariances in the spectral density are replaced by alternative dependence measures that can be estimated by U‐statistics. An interesting example is given by Kendall's τ, for which the limiting variance exhibits a surprising behavior.     

Interaction of Boron Carbide with Nickel Oxide

Thermodynamic methods and x-ray analysis have been applied to the chemical interactions in 0.9625 B₄C + 0.05 NiO + 0.0375 C, B₄C + NiO, B₄C + 4 NiO + 3 C mixtures; stages occur in the processes there that correspond to various temperature ranges. It is found that NiB always contains small amounts of lower borides, whose quantity does not exceed 2 mass% when the synthesis conditions are optimal.     

Single-neuron analysis using CE combined with MALDI MS and radionuclide detection

Capillary electrophoresis (CE) has been combined with matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) and radionuclide detection to assay mass-limited biological samples. Nanovial sampling techniques enable injections into the CE capillary from 50 to 150-nL volume samples; after the separation, nanoliter fraction collection combines the CE effluent with a MALDI matrix and minimizes sample spreading, thus allowing both MALDI MS and radionuclide detection on the CE fractions. MALDI MS complements the elution time information of CE by providing accurate molecular mass data, and radionuclide detection provides zeptomole limits of detection with quantitative information. While MALDI MS detects all fully processed peptides at sufficient concentration, culturing the neuron in media containing 35S-Met provides selective radionuclide detection of newly synthesized methionine-containing peptides. The analysis and detection of the expected neuropeptides and hormones in a single 40-microm bag cell neuron from Aplysia californica with CE/MALDI MS/radionuclide detection demonstrates the ability of this hyphenated approach to work with chemically complex mass-limited samples.