Optimized design of multilayer barrier films incorporating a reactive layer. III. Case analysis and generalized multilayer solutions

In part III of this series of articles, we present the analysis of transient permeation through two‐layer reactive–passive (RP) film designs, the analysis extension to multilayer structures, and optimized design solutions for multilayer barriers incorporating immobile noncatalytic oxygen scavenger within one of the layers. The reduction of oxygen ingress into a package within a certain timeframe depends on two factors: extension of the scavenger exhaustion time and reduction of the transient transmission rate through the film during that time. The optimal design for the scavenger exhaustion time involves exposure of the reactive layer to the package contents and its protection from high levels of environmental oxygen by the best possible passive barrier layer. The film barrier properties can be further optimized by the selection of the matrix material to place the scavenger in. Reducing the initial transmission rate requires the placement of the scavenger within a layer with the lowest diffusivity of the matrix polymer. When one chooses between two layers with different material transport properties in which to put the scavenger, the optimal solution for the ingress depends on the desired time to provide an improved barrier. The lifetime of the scavenger in the RP film is shortened for design 1, when the diffusivity of the reactive layer is smaller than that of the passive layer, compared to RP design 2, with the layer matrix sequence reversed, but the transient transmission rate is greatly reduced on average for the former. If the desired time to provide a barrier does not exceed the scavenger exhaustion time for RP design 1, the lowest diffusivity material should be used as a matrix for the innermost layer loaded with the scavenger. Otherwise, the highest possible passive barrier should be placed into the film external layer to minimize the total ingress during longer times. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1966–1977, 2006     

On gradual dosage of the initiator in the suspension polymerization of vinyl chloride

Initiator dosage in the solid phase during the suspension polymerization of vinyl chloride has been investigated with the use of a special apparatus developed for this purpose. Results arc reported on a series of polymerizations in which the initiator was divided in various ratios between the starting and additional quantities, added either in one dose or repeatedly to the reaction mixture at various reaction times. Discussed is the kinetic course of polymerization and the effect of dosage on the rate of reaction heat release. It is found for the system used that a suitable dosage regime allows the total amount of the initiator to be reduced by as much as 15 percent, while the yield and the reaction time corresponding to the standard polymerization procedure remain unchanged.     

Dielectric and piezoelectric properties of PbFe1/2Nb1/2O3-PbTiO3 ceramics from the morphotropic phase boundary compositional range

Dielectric, X-ray, and piezoelectric studies of highly-resistive Li-doped (1-x)PbFe(1/2)Nb(1/2)O(3)-(x)PbTiO(3) (PFN-xPT) ceramics from the 0 ≤ x ≤ 0.2 range fabricated by solid-state synthesis and usual sintering have been carried out. Distinct anomalies of dielectric and piezoelectric parameters, corresponding to the transition between rhombohedral (monoclinic) and tetragonal ferroelectric phases, have been observed in pure PFN and PFN-xPT compositions with PbTiO(3) content up to 8 mol.%. The x,T-phase diagram of the PFN-xPT solid solution system has been constructed using these data.     

Pulsed magneto-motive ultrasound imaging to detect intracellular trafficking of magnetic nanoparticles

As applications of nanoparticles in medical imaging and biomedicine rapidly expand, the interactions of nanoparticles with living cells have become an area of active interest. For example, intracellular accumulation of nanoparticles-an important part of cell-nanoparticle interaction-has been well studied using plasmonic nanoparticles and optical or optics-based techniques due to the change in optical properties of the nanoparticle aggregates. However, magnetic nanoparticles, despite their wide range of clinical applications, do not exhibit plasmonic-resonant properties and therefore their intracellular aggregation cannot be detected by optics-based imaging techniques. In this study, we investigated the feasibility of a novel imaging technique-pulsed magneto-motive ultrasound (pMMUS)-to identify intracellular accumulation of endocytosed magnetic nanoparticles. In pMMUS imaging a focused, high intensity, pulsed magnetic field is used to excite the cells labeled with magnetic nanoparticles, and ultrasound imaging is then used to monitor the mechanical response of the tissue. We demonstrated previously that clusters of magnetic nanoparticles amplify the pMMUS signal in comparison to the signal from individual nanoparticles. Here we further demonstrate that pMMUS imaging can identify interaction between magnetic nanoparticles and living cells, i.e.?intracellular accumulation of nanoparticles within the cells. The results of our study suggest that pMMUS imaging can not only detect the presence of magnetic nanoparticles but also provides information about their intracellular accumulation non-invasively and in real-time.     

Silver Stars: Silver–Polymer Composite Stars: Synthesis and Applications (Adv. Funct. Mater. 9/2011)

Colloidal “silver stars” were synthesized upon poly(lactic‐co‐glycolic) acid nanosphere templates via a facile two‐step silver reduction method. Myriad dendrimer‐like Ag star morphologies were synthesized by varying the amount of poly(vinyl alcohol) and trisodium citrate used during silver reduction. Scanning electron microscopy studies revealed that star‐shaped silver–polymer composites possessing nanoscopic, fractal morphologies with diameters ranging from 500 nm to 7 μm were produced. These composites have broad applications from antibacterial agents to catalysis; two such applications were tested here. Surface‐enhanced Raman spectroscopy (SERS) studies showed multiple hot spots of SERS activity within a single star. Electrochemical catalysis experiments demonstrated the feasibility of using the silver stars instead of platinum for the oxygen reduction reaction in alkaline fuel cells.     

Collection of peptides released from single neurons with particle-embedded monolithic capillaries followed by detection with matrix-assisted laser desorption/ionization mass spectrometry

Characterization of the stimulated release of neuropeptides from brain slices and individual cultured neurons requires efficient collection of the releasate from relatively large volumes of physiological saline. Here, several collection approaches are optimized using particle-embedded monolithic capillaries (PEMCs) with poly(stearyl methacrylate-co-ethylene glycol dimethacrylate) monolith acting as a "glue". Two distinct extraction particles, with either pyrrolidone (PY) or ethylenediamine (EDA) as the functional group on polystyrene backbone, have been embedded into capillaries having an inner diameter of 250 μm. The capillaries act as collection devices for sampling neuropeptide release; the collection protocols are described, and the extraction efficiency of the probes are characterized. Specifically, the binding of angiotensin II from a peptide mixture onto the PY and EDA columns was 16 and 28 pmol, respectively, in a volume of 20 μL of saline. The peptides released from these columns have been characterized via matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with low femtomole detection limits. When the PEMC columns were positioned in close proximity to individual neurons and 50 mM KCl was used as the secretagogue, peptides released from individual identified cultured neurons isolated from Aplysia californica were collected and characterized.     

Raman microscopy-based cytochemical investigations of potential niche-forming inhomogeneities present in human embryonic stem cell colonies

Measuring spatial and temporal patterns of cytochemical variation in human embryonic stem cell (hESC) colonies is necessary for understanding the role of cellular communication in spontaneous differentiation, the mechanisms of biological niche creation, and structure-generating developmental processes. Such insights will ultimately facilitate directed differentiation and therewith promote advances in tissue engineering and regenerative medicine. However, the patterns of cytochemical inhomogeneities of hESC colonies are not well studied and their causes are not fully understood. We used Raman spectroscopic mapping to contrast supracellular variations in cytochemical composition across pluripotent and partly differentiated hESC colonies to gain a better understanding of the early-stage (i.e., 5 days) effects of the differentiation process on the nature and evolution of these patterns. Higher protein-to-nucleic acid ratios, a differentiation status indicator observed previously using Raman spectroscopy, confirmed reported results that spontaneous differentiation is more pronounced on the edges of a colony than elsewhere. In addition, pluripotent and partly differentiated colonies also showed higher lipid concentrations relative to nucleic acids at colony edges in contrast to relative glycogen concentrations, which were up to 400% more pronounced in the colony centers compared to their edges. Pluripotent and partly differentiated colonies differed, with the latter having higher average protein-to-nucleic acid and lipid-to-nucleic acid ratios but a lower glycogen-to-nucleic acid ratio. In both cases, cell density, pluripotency, and high glycogen appeared to vary in tandem. Spatial variations in glycogen- and protein-to-nucleic acid ratios have features on the order of 100 μm and larger. These dimensions are consistent with those reported for stem cell niches and suggest that cytochemical inhomogeneities may provide colony-level information about niches and niche formation. These results demonstrate Raman mapping to be a potentially useful technique for revealing the complexities in the spatial organization of hESC cultures and thus for monitoring the evolution of engineered hESC niches.     

Analysis of geosynthetic tubes filled with several liquids with different densities

A two dimensional model of a geosynthetic tube sitting on a rigid horizontal foundation and filled with several separated liquids with different densities is proposed. The material from which the tube is made is a special synthetic fabric which is inextensible, perfectly flexible, and leakproof. Such a model is useful for modeling a consolidations process in the tube filled with a slurry. The equilibrium equations of the model are formulated. Unknown values like the pressure on the top and bottom of the tube, the tension in the geosynthetic fabric, the length of the contact zone between the tube and the rigid foundation are searched with respect to the given perimeter, the volumes and densities of liquids. Such a problem is solved by the Newton’s method. The initial approximation is obtained by solving a simplified problem with one liquid with the average density. The problem is implemented in a MATLAB code for geosynthetic tubes filled with two, three, and four liquids with different densities. The tubes filled with two different liquids are studied in more detail. The graphs of the relations are compared with the graphs for the tube filled with the single liquid whose density is the average of the densities of the liquids. The comparison enables to discuss the influence of the consolidation process on the height, the contact zone, the pressures and the tension of the tube. The results of the proposed model for a tube filled with a single liquid are compared with another model.     

Multimodal Magneto‐Plasmonic Nanoclusters for Biomedical Applications

Multimodal nanostructures can help solve many problems in the biomedical field including sensitive molecular imaging, highly specific therapy, and early cancer detection. However, the synthesis of densely packed, multicomponent nanostructures with multimodal functionality represents a significant challenge. Here, a new type of hybrid magneto‐plasmonic nanoparticles is developed using an oil‐in‐water microemulsion method. The nanostructures are synthetized by self‐assembly of primary 6 nm iron oxide core‐gold shell particles resulting into densely packed spherical nanoclusters. The dense packing of primary particles does not change their superparamagnetic behavior; however, the close proximity of the constituent particles in the nanocluster leads to strong near‐infrared (NIR) plasmon resonances. The synthesis is optimized to eliminate nanocluster cytotoxicity. Immunotargeted nanoclusters are also developed using directional conjugation chemistry through the Fc antibody moiety, leaving the Fab antigen recognizing region available for targeting. Cancer cells labeled with immunotargeted nanoclusters produce a strong photoacoustic signal in the NIR that is optimum for tissue imaging. Furthermore, the labeled cells can be efficiently captured using an external magnetic field. The biocompatible magneto‐plasmonic nanoparticles can make a significant impact in development of point‐of‐care assays for detection of circulating tumor cells, as well as in cell therapy with magnetic cell guidance and imaging monitoring.     

Fluctuation analysis and faradaic impedance at micro liquid/liquid interface—II

Tetramethylammonium, tetraethylammonium and cesium ion transfer reactions across the water/nitrobenzene micro-interface were studied by fluctuation analysis and ac impedance technique to elucidate the origin of micro-convections at the interface. It is shown that the effect of micro-convections on ion transfer process is enhanced by non-equilibrium conditions at the interface, ie by the existence of a mixed potential difference.