Miriam Rafailovich

Structural development during deformation of polyurethane containing polyhedral oligomeric silsesquioxanes (POSS) molecules

A unique polyurethane (PU) elastomer containing inorganic polyhedral oligomeric silsesquioxane (POSS) molecules as molecular reinforcements in the hard segment was investigated by means of wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) techniques. The mechanical properties of POSS modified polyurethane (POSS-PU) were also compared to those of polyurethane without POSS. The crystal structures of two different POSS molecules were first determined by X-ray powder diffraction analysis, yielding a rhombohedral cell with aa 11.57 A ˚, aa 95.58 for octacyclohexyl-POSS (1,3,5,7,9,11,13,15octacyclohexylpentacyclo[9.5.1.13,9.15,15.17,13] octasiloxane) and aa 11.53 A ˚, aa 95.38 for hydrido-POSS (1-[hydridodimethylsiloxy]3,5,7,9,11,13,15-heptacyclohexylpentacyclo [9.5.1.13,9.15,15.17,13] octasiloxane). WAXD results showed that reflection peaks distinct to POSS crystal diffraction were seen in POSS-modified polyurethane, which suggests that POSS molecules formed nanoscale crystals in the hard domain. During deformation, the average size of POSS crystals in POSS-PU was found to decrease while elongation-induced crystallization of the soft segments was observed at strains greater than 100%. The SAXS results showed microphase structure typical of segmented

Nanoscale reinforcement of polyhedral oligomeric silsesquioxane (POSS) in polyurethane elastomer

A unique class of polyurethane (PU) elastomer containing inorganic molecules (polyhedral oligomeric silsesquioxane, POSS) as molecular reinforcement in the hard segment was investigated by means of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. WAXD results indicate that POSS molecules form nanoscale crystals showing distinct reflection peaks. The formation of POSS crystals is probably prompted by the microphase separation between solid-like hard segments and rubbery soft segments in PU. The microphase separation of hard and soft segments was observed by SAXS, which shows a long period of 111 A for 34 wt% POSS-PU and 162 A for 21 wt% POSS-PU, and hard segment domains with sizes of about 34 A for both of them. WAXD results from a series of POSS compounds with a corner substituted by a functional group of varying length were compared with POSS-PU, which also confirms the presence of nanoscale POSS crystals in the polymer matrix. © 2000 Society of Chemical Industry

Adverse Effects of Titanium Dioxide Nanoparticles on Human Dermal Fibroblasts and How to Protect Cells

The effects of exposure of human dermal fibroblasts to rutile and anatase TiO(2) nanoparticles are reported. These particles can impair cell function, with the latter being more potent at producing damage. The exposure to nanoparticles decreases cell area, cell proliferation, mobility, and ability to contract collagen. Individual particles are shown to penetrate easily through the cell membrane in the absence of endocytosis, while some endocytosis is observed for larger particle clusters. Once inside, the particles are sequestered in vesicles, which continue to fill up with increasing incubation time till they rupture. Particles coated with a dense grafted polymer brush are also tested, and, using flow cytometry, are shown to prevent adherence to the cell membrane and hence penetration of the cell, which effectively decreases reactive oxygen species (ROS) formation and protects cells, even in the absence of light exposure. Considering the broad applications of these nanoparticles in personal health care products, the functionalized polymer coating can potentially play an important role in protecting cells and tissue from damage.

Coping with antibiotic resistance: combining nanoparticles with antibiotics and other antimicrobial agents

The worldwide escalation of bacterial resistance to conventional medical antibiotics is a serious concern for modern medicine. High prevalence of multidrug-resistant bacteria among bacteria-based infections decreases effectiveness of current treatments and causes thousands of deaths. New improvements in present methods and novel strategies are urgently needed to cope with this problem. Owing to their antibacterial activities, metallic nanoparticles represent an effective solution for overcoming bacterial resistance. However, metallic nanoparticles are toxic, which causes restrictions in their use. Recent studies have shown that combining nanoparticles with antibiotics not only reduces the toxicity of both agents towards human cells by decreasing the requirement for high dosages but also enhances their bactericidal properties. Combining antibiotics with nanoparticles also restores their ability to destroy bacteria that have acquired resistance to them. Furthermore, nanoparticles tagged with antibiotics have been shown to increase the concentration of antibiotics at the site of bacterium–antibiotic interaction, and to facilitate binding of antibiotics to bacteria. Likewise, combining nanoparticles with antimicrobial peptides and essential oils generates genuine synergy against bacterial resistance. In this article, we aim to summarize recent studies on interactions between nanoparticles and antibiotics, as well as other antibacterial agents to formulate new prospects for future studies. Based on the promising data that demonstrated the synergistic effects of antimicrobial agents with nanoparticles, we believe that this combination is a potential candidate for more research into treatments for antibiotic-resistant bacteria.

A potentiometric protein sensor built with surface molecular imprinting method.

Surface molecular imprinting, as compared to molecular imprinted bulk polymers, has the advantages of higher re-occupation percentage of the reception sites, fast response, integration of sensing element and transducer, etc. In this study, a potentiometric protein sensor was developed based on the surface molecular imprinting technique. Using the self-assembled monolayers of alkanethiol with hydroxyl terminal groups as the matrix material, and target protein molecules as the template, the sensing layer was created on the surface of the gold-coated silicon chip-an electrochemical transducer. Potentiometric measurement demonstrated that the sensor could selectively detect myoglobin or hemoglobin molecules, either with or without the presence of other protein molecules in the same solution.

Confinement-induced miscibility in polymer blends

The use of polymer thin films in technology is increasingly widespread—for example, as protective or lithographic surface coatings, or as active (electronic or optical) elements in device architectures. But it is difficult to generate films of polymer mixtures with homogeneous surface properties, because of the tendency of the polymers to phase-separate,. Copolymer compatibilizers can induce miscibility in polymer blends, but only with chemical components that are either close to a critical point in the phase diagram or which have an attractive interaction between them,. Instead of manipulating the chemical composition of the blend, we show here that complete mixing can be obtained in polymer blends by the physical effect of confinement in thin films. The compatibilization results from entropic inhibition of phase separation into micelles, owing to confinement. The result is an intimately mixed microemulsion with a perfectly flat surface and a two-dimensional maze-like structure with columnar domains that extend through the film.

Size-controlled synthesis and characterization of thiol-stabilized gold nanoparticles

Size-controlled synthesis of nanoparticles of less than a few nanometers in size is a challenge due to the spatial resolution limit of most scattering and imaging techniques used for their structural characterization. We present the self-consistent analysis of the extended x-ray absorption fine-structure (EXAFS) spectroscopy data of ligand-stabilized metal nanoclusters. Our method employs the coordination number truncation and the surface-tension models in order to measure the average diameter and analyze the structure of the nanoparticles. EXAFS analysis was performed on the two series of dodecanethiol-stabilized gold nanoparticles prepared by one-phase and two-phase syntheses where the only control parameter was the gold/thiol ratio xi, varied between 6:1 and 1:6. The two-phase synthesis resulted in the smaller particles whose size decreased monotonically and stabilized at 16 A when xi was lowered below 1:1. This behavior is consistent with the theoretically predicted thermodynamic limit obtained previously in the framework of the spherical drop model of Au nanoparticles.

Antileishmanial effect of silver nanoparticles and their enhanced antiparasitic activity under ultraviolet light

Leishmaniasis is a protozoan vector-borne disease and is one of the biggest health problems of the world. Antileishmanial drugs have disadvantages such as toxicity and the recent development of resistance. One of the best-known mechanisms of the antibacterial effects of silver nanoparticles (Ag-NPs) is the production of reactive oxygen species to which Leishmania parasites are very sensitive. So far no information about the effects of Ag-NPs on Leishmania tropica parasites, the causative agent of leishmaniasis, exists in the literature. The aim of this study was to investigate the effects of Ag-NPs on biological parameters of L. tropica such as morphology, metabolic activity, proliferation, infectivity, and survival in host cells, in vitro. Consequently, parasite morphology and infectivity were impaired in comparison with the control. Also, enhanced effects of Ag-NPs were demonstrated on the morphology and infectivity of parasites under ultraviolet (UV) light. Ag-NPs demonstrated significant antileishmanial effects by inhibiting the proliferation and metabolic activity of promastigotes by 1.5- to threefold, respectively, in the dark, and 2- to 6.5-fold, respectively, under UV light. Of note, Ag-NPs inhibited the survival of amastigotes in host cells, and this effect was more significant in the presence of UV light. Thus, for the first time the antileishmanial effects of Ag-NPs on L. tropica parasites were demonstrated along with the enhanced antimicrobial activity of Ag-NPs under UV light. Determination of the antileishmanial effects of Ag-NPs is very important for the further development of new compounds containing nanoparticles in leishmaniasis treatment.

The Form of the Enriched Surface Layer in Polymer Blends

The concentration profile at the surface in blends of deuterated and protonated polystyrene (d-PS and PS) is inferred from measurements of neutron reflectivity and secondary-ion mass spectrometry, using constraints provided by forward recoil spectrometry and X-ray reflectometry results on the same samples. The surface is enriched in d-PS, the volume fraction and the decay length of which are in good agreement with the predictions of mean-field theory but the form of the profile shows small, but statistically significant, deviations from that predicted by the theory.

Effects of fiber orientation and diameter on the behavior of human dermal fibroblasts on electrospun PMMA scaffolds.

We used the electrospinning technique to produce fibrous scaffolds of poly(methyl methacrylate) (PMMA). Using a rotating drum, we aligned the fibers and formed multilayered structures where both the fiber spacing and pore size could be varied. We then plated adult human dermal fibroblasts and studied the effect of fiber diameter and orientation on the cell conformation, integrin receptor expression, proliferation, and migration. We found that a critical diameter minimum diameter existed, D0 = 0.97 microm for cell orientation to occur. For D < D0, no big difference in aspect ratio was observed relative to the control samples on PMMA thin film. Hence, we could fabricate substrate patterned with fibers of different diameters where different cell conformations coexisted on the same scaffold. On the other hand, staining for vinculin proteins in the cells indicated that on large diameter fibers and on flat surfaces, the integrin receptors followed the cell perimeter. On the very small diameter surfaces, the receptors were distributed uniformly along the cell. Cell dynamics studies indicated that the proliferation and migration were also affected by the fiber orientation.