Deniz Rende

Polymer nanocomposite foams

Polymer nanocomposite foams, polymer foams with nanoparticles, are an intriguing class of materials with unique structure and properties. The shape, size and surface chemistry of nanoparticles can be tailored to control the foam structure, and therefore, foam properties. Nanoparticles also add functionality to polymer foams. In this paper, we briefly review the recent developments in polymer nanocomposites and nanocomposite foams. This is followed by an extensive discussion regarding the role of nanoparticles in foam morphology and properties. Finally, the current and future trends of polymer nanocomposite foams are summarized. Both challenges and opportunities in this field are discussed.

Effect of Surface Modification on Magnetization of Iron Oxide Nanoparticle Colloids

Magnetic iron oxide nanoparticles have numerous applications in the biomedical field, some more mature, such as contrast agents in magnetic resonance imaging (MRI), and some emerging, such as heating agents in hyperthermia for cancer therapy. In all of these applications, the magnetic particles are coated with surfactants and polymers to enhance biocompatibility, prevent agglomeration, and add functionality. However, the coatings may interact with the surface atoms of the magnetic core and form a magnetically disordered layer, reducing the total amount of the magnetic phase, which is the key parameter in many applications. In the current study, amine and carboxyl functionalized and bare iron oxide nanoparticles, all suspended in water, were purchased and characterized. The presence of the coatings in commercial samples was verified with X-ray photoelectron spectroscopy (XPS). The class of iron oxide (magnetite) was verified via Raman spectroscopy and X-ray diffraction. In addition to these, in-house prepared iron oxide nanoparticles coated with oleic acid and suspended in heptane and hexane were also investigated. The saturation magnetization obtained from vibrating sample magnetometry (VSM) measurements was used to determine the effective concentration of magnetic phase in all samples. The Tiron chelation test was then utilized to check the real concentration of the iron oxide in the suspension. The difference between the concentration results from VSM and the Tiron test confirmed the reduction of magnetic phase of magnetic core in the presence of coatings and different suspension media. For the biocompatible coatings, the largest reduction was experienced by amine particles, where the ratio of the effective weight of magnetic phase reported to the real weight was 0.5. Carboxyl-coated samples experienced smaller reduction with a ratio of 0.64. Uncoated sample also exhibits a reduction with a ratio of 0.6. Oleic acid covered samples show a solvent-depended reduction with a ratio of 0.5 in heptane and 0.4 in hexane. The corresponding effective thickness of the nonmagnetic layer between magnetic core and surface coating was calculated by fitting experimentally measured magnetization to the modified Langevin equation.

Sulfated levan from Halomonas smyrnensis as a bioactive, heparin-mimetic glycan for cardiac tissue engineering applications.

Chemical derivatives of levan from Halomonas smyrnensis AAD6(T) with low, medium and high levels of sulfation were synthesized and characterized by FTIR and 2D-NMR. Sulfated levan samples were found to exhibit anticoagulation activity via the intrinsic pathway like heparin in a dose-dependent manner. Exceptionally high heparin equivalent activity of levan sulfate was shown to proceed via thrombin inhibition where decreased Factor Xa activity with increasing concentration was observed in antithrombin tests and above a certain concentration, levan sulfate showed a better inhibitor activity than heparin. In vitro experimental results were then verified in silico by docking studies using equilibrium structures obtained by molecular dynamic simulations and results suggested a sulfation dependent binding mechanism. With its high biocompatibility and heparin mimetic activity, levan sulfate can be considered as a suitable functional biomaterial to design biologically active, functionalized, thin films and engineered smart scaffolds for cardiac tissue engineering applications.

A novel integrative network approach to understand the interplay between cardiovascular disease and other complex disorders.

There is accumulating evidence that the proteins encoded by the genes associated with a common disorder interact with each other, participate in similar pathways and share GO terms. It has been anticipated that the functional modules in a disease related functional linkage network can be integrated with bibliomics to reveal association with other complex disorders. In this study, the cardiovascular disease functional linkage network (CFN) containing 1536 nodes and 3345 interactions was constructed using proteins encoded by 234 genes associated with the disease. Integration of CFN with bibliomics showed that 227 out of 566 functional modules are significantly associated with one or more diseases. Analysis of functional modules revealed the possible regulatory roles of SP1 and CXCL12 in the pathogenesis of cardiovascular disease (CVD) and modulation of their activities may be considered as potential therapeutic tools. The integration of CFN with bibliomics also indicated significant relations of CVD with other complex disorders. In a stratified map the members of 227 functional modules and 58 diseases in 15 disease classes were combined. In this map, leprosy, listeria monocytogenes, myasthenia, hemorrhagic diathesis and Protein S deficiency, which were not previously reported to be associated with CVD, showed significant associations. Several cancers arising from epithelial cells were also found to be linked to other diseases through hub proteins, VEGFA and PTGS2.

Controlling Foam Morphology of Poly(methyl methacrylate) via Surface Chemistry and Concentration of Silica Nanoparticles and Supercritical Carbon Dioxide Process Parameters

Polymer nanocomposite foams have received considerable attention because of their potential use in advanced applications such as bone scaffolds, food packaging, and transportation materials due to their low density and enhanced mechanical, thermal, and electrical properties compared to traditional polymer foams. In this study, silica nanofillers were used as nucleating agents and supercritical carbon dioxide as the foaming agent. The use of nanofillers provides an interface upon which CO2 nucleates and leads to remarkably low average cell sizes while improving cell density (number of cells per unit volume). In this study, the effect of concentration, the extent of surface modification of silica nanofillers with CO2-philic chemical groups, and supercritical carbon dioxide process conditions on the foam morphology of poly(methyl methacrylate), PMMA, were systematically investigated to shed light on the relative importance of material and process parameters. The silica nanoparticles were chemically modified with tridecafluoro-1,1,2,2-tetrahydrooctyl triethoxysilane leading to three different surface chemistries. The silica concentration was varied from 0.85 to 3.2% (by weight). The supercritical CO2 foaming was performed at four different temperatures (40, 65, 75, and 85°C) and between 8.97 and 17.93 MPa. By altering the surface chemistry of the silica nanofiller and manipulating the process conditions, the average cell diameter was decreased from to  μm, whereas, the cell density was increased from to cells/cm3. Our findings indicate that surface modification of silica nanoparticles with CO2-philic surfactants has the strongest effect on foam morphology.

Reduced astrocyte viability at physiological temperatures from magnetically activated iron oxide nanoparticles.

Superparamagnetic iron oxide nanoparticles (SPIONs) can generate heat when subjected to an alternating magnetic field (AMF). In the European Union, SPIONs actuated by AMF are used in hyperthermia treatment of glioblastoma multiforme, an aggressive form of brain cancer. Current data from clinical trials suggest that this therapy improves patient life expectancy, but their effect on healthy brain cells is virtually unknown. Thus, a viability study involving SPIONs subjected to an AMF was carried out on healthy cortical rat astrocytes, the most abundant cell type in the mammalian brain. The cells were cultured with aminosilane- or starch-coated SPIONs with or without application of an AMF. Significant cell death (p < 0.05) was observed only when SPIONs were added to astrocyte cultures and subjected to an AMF. Unexpectedly, the decrease in astrocyte viability was observed at physiological temperatures (34-40 °C) with AMF. A further decrease in astrocyte viability was found only when bulk temperatures exceeded 45 °C. To discern differences in the astrocyte structure when astrocytes were cultured with particles with or without AMF, scanning electron microscopy (SEM) was performed. SEM images revealed a change in the structure of the astrocyte cell membrane only when astrocytes were cultured with SPIONs and actuated with an AMF. This study is the first to report that astrocyte death occurs at physiological temperatures in the presence of magnetic particles and AMF, suggesting that other mechanisms are responsible for inducing astrocyte death in addition to heat.

Complex Disease Interventions from a Network Model for Type 2 Diabetes

There is accumulating evidence that the proteins encoded by the genes associated with a common disorder interact with each other, participate in similar pathways and share GO terms. It has been anticipated that the functional modules in a disease related functional linkage network are informative to reveal significant metabolic processes and disease’s associations with other complex disorders. In the current study, Type 2 diabetes associated functional linkage network (T2DFN) containing 2770 proteins and 15041 linkages was constructed. The functional modules in this network were scored and evaluated in terms of shared pathways, co-localization, co-expression and associations with similar diseases. The assembly of top scoring overlapping members in the functional modules revealed that, along with the well known biological pathways, circadian rhythm, diverse actions of nuclear receptors in steroid and retinoic acid metabolisms have significant occurrence in the pathophysiology of the disease. The disease’s association with other metabolic and neuromuscular disorders was established through shared proteins. Nuclear receptor NRIP1 has a pivotal role in lipid and carbohydrate metabolism, indicating the need to investigate subsequent effects of NRIP1 on Type 2 diabetes. Our study also revealed that CREB binding protein (CREBBP) and cardiotrophin-1 (CTF1) have suggestive roles in linking Type 2 diabetes and neuromuscular diseases.

Evaluation of procedures to quantify solvent retention in electrospun fibers and facilitate solvent removal

Electrospun fiber scaffolds crafted from polyesters are studied extensively for potential tissue engineering applications. For translation of electrospun fibers into the clinic, the FDA requires analysis and quantification of any organic solvent that may be retained in the fibers since many organic solvents can negatively affect cells and tissues. If a significant amount of solvent is retained, then developing procedures for efficient solvent removal may enhance the clinical potential of these materials. In this study we use fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and nuclear magnetic resonance spectroscopy (NMR) to analyze solvent retention. A correlative analysis shows that both FTIR and TGA accurately predicted retention of two different solvents (HFP and chloroform) in our electrospun PLLA scaffolds, thus validating these procedures. We also assess the efficacy of various fiber treatment methods to facilitate organic solvent removal and conclude that submersion in 70 % ethanol and heat treatment at 100 °C were the most efficient methods of removing solvent from electrospun PLLA fibers.

Interfacial surfactant competition and its impact on poly(ethylene oxide)/Au and poly(ethylene oxide)/Ag nanocomposite properties

The structure and properties of nanocomposites of poly(ethylene oxide), with Ag and Au nanoparticles, surface modified with a 1:1 (by volume) oleylamine/oleic acid mixture, were investigated via transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), infrared spectroscopy, dynamic mechanical analysis, and static mechanical testing. Results indicated that there was more oleylamine on Ag nanoparticles but more oleic acid on Au nanoparticles. This difference in surfactant populations on each nanoparticle led to different interfacial interactions with poly(ethylene oxide) and drastically influenced the glass transition temperature of these two nanocomposite systems. Almost all other properties were found to correlate strongly with dispersion and distribution state of Au and Ag nanoparticles, such that the property in question changed direction at the onset of agglomeration.

WikiLeaks on the Middle East: Obscure Diplomacy Networks and Binding Spaces

In this paper, we explore the flow of information regarding strategic Middle Eastern countries in the WikiLeaks ‘diplomatic cables’ by applying data-mining techniques to construct directed networks. The results show that between 2002 and 2009, US diplomatic communication related to these countries increased although with notable variation in flow patterns. We discuss the value of a visual display of diplomatic communication patterns in understanding the decentralized nature of information gathering on regional foreign policy issues.