23 research outputs found
MicroRNA‐146 represses endothelial activation by inhibiting pro‐inflammatory pathways
Activation of inflammatory pathways in the endothelium contributes to vascular diseases, including sepsis and atherosclerosis. We demonstrate that miR-146a and miR-146b are induced in endothelial cells upon exposure to pro-inflammatory cytokines. Despite the rapid transcriptional induction of the miR-146a/b loci, which is in part mediated by EGR-3, miR-146a/b induction is delayed and sustained compared to the expression of leukocyte adhesion molecules, and in fact coincides with the down-regulation of inflammatory gene expression. We demonstrate that miR-146 negatively regulates inflammation. Over-expression of miR-146a blunts endothelial activation, while knock-down of miR-146a/b in vitro or deletion of miR-146a in mice has the opposite effect. MiR-146 represses the pro-inflammatory NF-κB pathway as well as the MAP kinase pathway and downstream EGR transcription factors. Finally, we demonstrate that HuR, an RNA binding protein that promotes endothelial activation by suppressing expression of endothelial nitric oxide synthase (eNOS), is a novel miR-146 target. Thus, we uncover an important negative feedback regulatory loop that controls pro-inflammatory signalling in endothelial cells that may impact vascular inflammatory diseases
Enhanced control of plasmonic properties of silver-gold hollow nanoparticles via a reduction-assisted galvanic replacement approach.
Hollow noble metal nanoparticles are of growing interest due to their localized surface plasmon resonance (LSPR) tunability. A popular synthetic approach is galvanic replacement which can be coupled with a co-reducer. Here, we describe the control over morphology, and therefore over plasmonic properties including energy, bandwidth, extinction and scattering intensity, offered by co-reduction galvanic replacement. This study indicates that whereas the variation of atomic stoichiometry using the co-reduction method described in this work offers a rather modest tuning range of LSPR energy when compared to traditional galvanic replacement, it nevertheless has a profound effect on shell thickness, which imparts a degree of control over scattering intensity and sensitivity to changes in the dielectric constant of the surrounding environment. Therefore, in this context particle size and gold content become two design parameters that can be used to independently tune LSPR energy and intensity.This research was supported by the American Chemical Society Petroleum Research Fund under grant number 56256 DNI5 (E. R.) and a 3M Nontenured Faculty Award (E. R.). L. A. M. wishes to acknowledge financial support from a National Science Foundation Graduate Research Fellowship #1450681. D. B. and J. R. D. acknowledge funding from the Natural Sciences and Engineering Research Council of Canada, the Canadian Foundation for Innovation and the Fonds de la Recherche du Québe
Enhanced control of plasmonic properties of silver–gold hollow nanoparticles via a reduction-assisted galvanic replacement approach
Hollow noble metal nanoparticles are of growing interest due to their localized surface plasmon resonance (LSPR) tunability. A popular synthetic approach is galvanic replacement which can be coupled with a co-reducer. Here, we describe the control over morphology, and therefore over plasmonic properties including energy, bandwidth, extinction and scattering intensity, offered by co-reduction galvanic replacement. This study indicates that whereas the variation of atomic stoichiometry using the co-reduction method described in this work offers a rather modest tuning range of LSPR energy when compared to traditional galvanic replacement, it nevertheless has a profound effect on shell thickness, which imparts a degree of control over scattering intensity and sensitivity to changes in the dielectric constant of the surrounding environment. Therefore, in this context particle size and gold content become two design parameters that can be used to independently tune LSPR energy and intensity
Recommended from our members
Reversible Shape and Plasmon Tuning in Hollow AgAu Nanorods.
The internal structure of hollow AgAu nanorods created by partial galvanic replacement was manipulated reversibly, and its effect on optical properties was mapped with nanometer resolution. Using the electron beam in a scanning transmission electron microscope to create solvated electrons and reactive radicals in an encapsulated solution-filled cavity in the nanorods, Ag ions were reduced nearby the electron beam, reshaping the core of the nanoparticles without affecting the external shape. The changes in plasmon-induced near-field properties were then mapped with electron energy-loss spectroscopy without disturbing the internal structure, and the results are supported by finite-difference time-domain calculations. This reversible shape and near-field control in a hollow nanoparticle actuated by an external stimulus introduces possibilities for applications in reprogrammable sensors, responsive materials, and optical memory units. Moreover, the liquid-filled nanorod cavity offers new opportunities for in situ microscopy of chemical reactions
Gold Speciation and Co-reduction Control the Morphology of AgAu Nanoshells in Formaldehyde-Assisted Galvanic Replacement
Hollow AgAu nanostructures have a myriad of potential applications related to their strong and tunable localized surface plasmon resonances. Here, we describe how the hydrolysis of the Au precursor, AuCl4–, produces AuCl4–x(OH)x–, where x is both time and pH-dependent, and how this can be used to control the morphology of hollow nanoshells in the co-reduction-assisted galvanic replacement of Ag by Au. Controlling the degree of hydrolysis is the key to obtain smooth shells: too small values of x (low hydrolysis) yield inhomogeneously replaced rough shells whereas too large values of x lead to the dominance of Au nucleation over galvanic replacement. Kinetic studies reveal two time constants for the galvanic replacement varying with temperature and composition; a short (100 min) half-life component associated with the continuous reduction and replacement of Ag. By optimizing the reaction’s pH and Au speciation, we obtained smooth alloy shells with fine control of composition, size, and shape over a broad range, thereby tuning the optical properties. This framework for understanding and controlling reaction kinetics and nanoshell morphology is applicable to other metallic systems and precursors, providing new ways to rationally design nanostructure syntheses
Gold speciation and co-reduction control the morphology of AgAu nanoshells in formaldehyde-assisted galvanic replacement
Hollow AgAu nanostructures have a myriad of potential applications related to their strong and tunable localized surface plasmon resonances. Here, we describe how the hydrolysis of the Au precursor, AuCl4–, produces AuCl4–x(OH)x–, where x is both time and pH-dependent, and how this can be used to control the morphology of hollow nanoshells in the co-reduction-assisted galvanic replacement of Ag by Au. Controlling the degree of hydrolysis is the key to obtain smooth shells: too small values of x (low hydrolysis) yield inhomogeneously replaced rough shells whereas too large values of x lead to the dominance of Au nucleation over galvanic replacement. Kinetic studies reveal two time constants for the galvanic replacement varying with temperature and composition; a short (100 min) half-life component associated with the continuous reduction and replacement of Ag. By optimizing the reaction’s pH and Au speciation, we obtained smooth alloy shells with fine control of composition, size, and shape over a broad range, thereby tuning the optical properties. This framework for understanding and controlling reaction kinetics and nanoshell morphology is applicable to other metallic systems and precursors, providing new ways to rationally design nanostructure syntheses