Comparative study of guest charge-charge interactions within silica sol-gel.

Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, USA.
The Journal of Physical Chemistry B (Impact Factor: 3.61). 04/2005; 109(11):4816-23. DOI: 10.1021/jp0458957
Source: PubMed

ABSTRACT We investigated the effect of charge-charge interactions on the mobilities of rhodamine 6G (R6G), Nile Red, sulforhodamine B, and Oregon Green 514 (ORG) guest molecules within a silica sol-gel host as the guest charge progressed from positive to neutral to negative. Through classification of the mobility as fixed, tumbling, or intermediate behavior, we were able to distinguish differences in surface attraction as the guest charge was varied. On the basis of our results, an attractive charge (as tested by cationic R6G) does not contribute significantly to mobility within dry films. However, an increase in the cationic influence is observed in water-equilibrated environments. A comparison of ORG in dry and water- and phosphate-buffer-equilibrated films indicates that charge repulsion does significantly increase dye rotational mobility (to a maximum of 24 +/- 3% tumbling molecules). However, in view of the percentage of tumbling molecules found, charge-charge interactions do not appear to be the dominant force controlling guest mobility.

  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Nanomaterials such as SiO2 nanoparticles (SiO2NP) are finding increasing applications in the biomedical and biotechnological fields such as disease diagnostics, imaging, drug delivery, food, cosmetics and biosensors development. Thus, a mechanistic and systematic evaluation of the potential biological and toxic effects of SiO2NP becomes crucial in order to assess their complete safe applicability limits. In this study, human monocytic leukemia cell line THP-1 and human alveolar epithelial cell line A549 were exposed to a range of amorphous SiO2NP of various sizes and concentrations (0.01, 0.1 and 0.5 mg/ml). Key biological indicators of cellular functions including cell population density, cellular morphology, membrane permeability, lysosomal mass/pH and activation of transcription factor-2 (ATF-2) were evaluated utilizing quantitative high content screening (HCS) approach and biochemical techniques. Despite the use of extremely high nanoparticle concentrations, our findings showed a low degree of cytotoxicity within the panel of SiO2NP investigated. However, at these concentrations, we observed the onset of stress-related cellular response induced by SiO2NP. Interestingly, cells exposed to alumina-coated SiO2NP showed low level, and in some cases complete absence, of stress response and this was consistent up to the highest dose of 0.5 mg/ml. The present study demonstrates and highlights the importance of subtle biological changes downstream of primary membrane and endocytosis-associated phenomena resulting from high dose SiO2NP exposure. Increased activation of transcription factors, such as ATF-2, was quantitatively assessed as a function of i) human cell line specific stress-response, ii) SiO2NP size and iii) concentration. Despite the low level of cytotoxicity detected for the amorphous SiO2NP investigated, these findings prompt an in-depth focus for future SiO2NP-cell/tissue investigations based on the combined analysis of more subtle signalling pathways associated with accumulation mechanisms, which is essential for establishing the bio-safety of existing and new nanomaterials.
    Journal of Nanobiotechnology 07/2011; 9:29. · 5.09 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: This study reports on the development and characterization of bacterial cellulose (BCNW) films coated with hydrophobic layers, presenting enhanced barrier properties. Pure BCNW films showed good transparency and thermal stability, high rigidity and extremely low oxygen permeability at 0%RH. The dramatic increase in oxygen permeability at 80%RH, due to the hydrophilic character of BCNW, was counteracted through coating the films with annealed PLA electrospun nanostructured fibres or hydrophobic silanes. The use of electrospinning was crucial to attain a good adhesion between the hydrophilic BCNW and the hydrophobic PLA layer. After electrospinning, the fibres were homogenised by annealing, thus obtaining a uniform and continuous coating. Coated systems showed a hydrophobic surface and protected the BCNW from moisture, thus reducing ca. 70% the water permeability and up to 97% the oxygen permeability at 80%RH. Furthermore, this novel approach was seen to protect BCNW films from moisture more efficiently than coating with hydrophobic silanes.
    Carbohydrate polymers. 10/2013; 98(1):1072-82.
  • [Show abstract] [Hide abstract]
    ABSTRACT: Single molecule spectroscopic methods are now being widely employed to probe the nanometer scale properties of sol-gel-derived silica materials. This article reviews a subset of the recent literature in this area and provides salient examples of the new information that can be obtained. The materials covered include inorganic and organically-modified silica, along with surfactant-templated mesoporous materials. Studies of molecule-matrix interactions based on ionic, hydrogen bonding and hydrophobic interactions are reviewed, highlighting the impacts of these interactions on mass transport phenomena. Quantitative investigations of molecular diffusion by single molecule tracking and fluorescence correlation spectroscopy are also covered, focusing on the characterization of anisotropic and hindered diffusion in mesoporous systems. Single molecule polarity studies are described and the new information that can be obtained from the resulting inhomogeneous distributions is discussed. Likewise, single molecule studies of silica acidity properties are reviewed, including observation of nanoscale buffering phenomena due to the chemistry of surface silanols. Finally, related single nanoparticle studies of macroporous silicas are also discussed.
    Physical Chemistry Chemical Physics 02/2009; 11(1):66-82. · 3.83 Impact Factor