Beating cancer in multiple ways using nanogold

Gold nanoparticles possess a unique combination of properties which allow them to act as highly multifunctional anti-cancer agents (X. H. Huang, P. K. Jain, I. H. El-Sayed and M. A. El-Sayed, Nanomedicine, 2007, 2, 681-693; P. Ghosh, G. Han, M. De, C. K. Kim and V. M. Rotello, Adv. Drug Delivery Rev., 2008, 60, 1307-1315; S. Lal, S. E. Clare and N. J. Halas, Acc. Chem. Res., 2008, 41, 1842-1851; D. A. Giljohann, D. S. Seferos, W. L. Daniel, M. D. Massich, P. C. Patel and C. A. Mirkin, Angew. Chem., Int. Ed., 2010, 49, 3280-3294). Not only can they be used as targeted contrast agents for photothermal cancer therapy, they can serve as scaffolds for increasingly potent cancer drug delivery, as transfection agents for selective gene therapy, and as intrinsic antineoplastic agents. This tutorial review will highlight some of the many forms and recent applications of these gold nanoparticle conjugates by our lab and others, as well as their rational design and physiologic interactions.     

Facile synthesis of TiO2 inverse opal electrodes for dye-sensitized solar cells

Engineering of TiO(2) electrode layers is critical to guaranteeing the photoconversion efficiency of dye-sensitized solar cells (DSSCs). Recently, a novel approach has been introduced for producing TiO(2) electrodes using the inverted structures of colloidal crystals. This paper describes a facile route to producing ordered macroporous electrodes from colloidal crystal templates for DSSCs. Using concentrated colloids dispersed in a volatile medium, the colloidal crystal templates were obtained within a few minutes, and the thickness of the template was easily controlled by changing the quantity of colloidal solution deposited. Here, the effects of the structural properties of the inverse opal TiO(2) electrodes on the photovoltaic parameters of DSSCs were investigated. The photovoltaic parameters were measured as a function of pore ordering and electrode film thickness. Moreover, DSSC applications that used either liquid or viscous polymer electrolyte solutions were investigated to reveal the effects of pore size on performance of an inverse opal TiO(2) electrode.     

Adsorption of lead(II) ions from aqueous solution on low-temperature exfoliated graphene nanosheets

Graphene nanosheets (GNSs) that were obtained by vacuum-promoted low-temperature exfoliation were used to adsorb lead ions from an aqueous system. The pristine and thermally modified GNSs were characterized with scanning electron microscopy observation and X-ray photoelectron spectroscopy analysis. It was interestingly found that the adsorption against lead ions was enhanced by heat treatment, although the oxygen complexes of GNSs showed a significant decrease. In addition, lead ion uptake resulted in an increase in the pH value of the solution. It is supposed that the Lewis basicity of GNSs is improved by heat treatment under a high vacuum, in favor of simultaneous adsorption of lead ions and protons onto GNSs.     

Strong response of multilayer polyelectrolyte films to cationic surfactants

The influence of common cationic surfactants on the physical properties of differently composed polyelectrolyte films prepared by the layer-by-layer (LbL) technology was investigated. Free-standing polyelectrolyte films as microcapsules showed a fast, strong response to the addition of less than 1 mM cationic surfactant cetyltrimethylammonium bromide (CeTAB). As a function of the polyelectrolyte composition, the behavior of the capsules varied from negligible changes to complete disintegration via strong swelling. The response of microcapsules consisting of (poly(allylamine hydrochloride)(PAH)/poly(styrene sulfonate)(PSS))(4) was associated with a 5-fold volume increase, a fast switch of permeability, and in the case of fluorescently labeled films a 4-fold increase in fluorescence intensity. The kinetics and strengths of the interaction process were investigated by confocal laser scanning microscopy (CLSM) and fluorescence spectroscopy. Also, the relative stabilities of the polycation/polyanion and surfactant/polyanion complexes were determined. A mechanism was suggested to explain the interactions between the cationic surfactants and polyelectrolyte capsules. The strong response can be exploited in potential applications such as the triggered release of drugs or other encapsulated materials, the fluorescence-based detection of cationic detergents, and a switchable stopper in microchannels. However, the high sensitivity of LbL films to traces of cationic surfactants can also limit their applicability to the encapsulation of drugs or other materials because pharmaceutical or technical formulations often contain cationic surfactants as preservatives such as benzalkonium salts (BAC). It was demonstrated that undesired capsule opening can be effectively prevented by cross-linking the polyelectrolyte multilayers.     

Biomimetic anchors for antifouling and antibacterial polymer brushes on stainless steel

Barnacle cement (BC) was beneficially applied on stainless steel (SS) to serve as the initiator anchor for surface-initiated polymerization. The amine and hydroxyl moieties of barnacle cement reacted with 2-bromoisobutyryl bromide to provide the alkyl halide initiator for the surface-initiated atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate (HEMA). The hydroxyl groups of HEMA polymer (PHEMA) were then converted to carboxyl groups for coupling of chitosan (CS) to impart the SS surface with both antifouling and antibacterial properties. The surface-functionalized SS reduced bovine serum albumin adsorption, bacterial adhesion, and exhibited antibacterial efficacy against Escherichia coli (E. coli). The effectiveness of barnacle cement as an initiator anchor was compared to that of dopamine, a marine mussel inspired biomimetic anchor previously used in surface-initiated polymerization. The results indicate that the barnacle cement is a stable and effective anchor for functional surface coatings and polymer brushes.     

Polyol-mediated solvothermal synthesis and luminescence properties of CeF3, and CeF3:Tb nanocrystals

CeF₃ and CeF₃:Tb³⁺ nanocrystals were successfully synthesized through a facile and effective polyol-mediated route with ethylene glycol (EG) as solvent. Various experimental techniques including X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and photoluminescence (PL) spectra as well as decay dynamics were used to characterize the samples. The results indicated that the content of NH₄F and reactant concentrations were key factors in the product shape and size. Excessive NH₄F was necessary for the formation of hexagonal nanoplates. The specific morphology of product can be controlled by changing the NH₄F content and reactant concentrations. In addition, Tb³⁺ doped-CeF₃ sample shows strong green emission centered at 544 nm corresponding to the ⁵D₄-⁷F₅ transition of Tb³⁺. Due to the decrease of nonradiative decay rate, the lifetime of ⁵D₄ level of Tb³⁺ become longer gradually upon increasing the size of product.     

Intrinsic magnetism in Fe doped SnO2 nanoparticles

Iron doped semiconducting nanoparticles Sn_1−xFe_xO₂ with x=0, 0.001, 0.002, 0.003, 0.004, 0.01 and 0.03 were prepared by a sol-gel method. The X-ray diffraction, Transmission Electron Microscopy measurements confirm the rutile structure with no impurity phase. The three characteristic lines of electron spin resonance (ESR) are observed in the doped samples for all compositions, which is a clear evidence for rhombic Fe³⁺ in rutile phase. The line width of ESR increases with increase in Fe concentration due to induced disorder. The spin-pumping effect is observed at temperatures below 250 K for the samples with x=0.01 and 0.03. However, based on the Curie-Weiss susceptibility, iron is in paramagnetic state and is subject to weak antiferromagnetic interaction. Blue shift in the optical band gap is observed with increase in the Fe content.     

Enzyme digestion of entrapped single-DNA molecules in nanopores

The real-time digestion of entrapped single-DNA molecules by λ-exonuclease in nanoporous alumina membranes was observed using an epifluorescence microscope. The alumina membrane provides pL (∼10⁻¹² L) containers for confining single-DNA molecules without immobilization. When one end of the DNA molecule was inserted into a nanopore, it was possible to monitor the digestion process outside, near and inside the pore, where the individual DNA molecules exhibited different characteristic digestion modes. The digestion rates calculated from the decrease in fluorescence intensity showed different values according to the location of the individual molecules. Entrapment rather than immobilization allows the DNA strand to be fully exposed to the enzyme and the reaction buffer. These results confirm that the enzymatic digestion of DNA molecules is affected by their three-dimensional (3D) environment.     

Production of Lactate in <Emphasis Type="Italic">Escherichia coli</Emphasis> by Redox Regulation Genetically and Physiologically

Escherichia coli grows fermentatively in glucose-containing medium under anaerobic condition with formation of a mixture of organic acids (lactate, acetate, formate, and succinate) and ethanol to accommodate reducing equivalents generated during glycolysis. In this paper, we tried to improve the lactate accumulation in E. coli by redox regulation genetically and physiologically. Our results indicated that genetic regulation of the host by reducing the reductive by-product may improve the lactate production. In addition, lactate accumulation was also improved under reduced and anaerobic cultivation conditions. Engineered E. coli SDU4 was able to accumulate lactate under strictly anaerobic conditions to 100 g/L with a yield of 1.97 mol/mol glucose.