Microcontact deprinting: A technique to pattern gold nanoparticles

A simple and general patterning technique for inorganic nanoparticles (NPs, e.g., gold NPs) is demonstrated, consisting of the selective lift-off of metal precursor loaded block copolymer micelles. The procedure works as follows: first, a topographically micropatterned polystyrene (PS) stamp is placed in contact with a substrate covered with hexagonally arranged micelles. Then the assembly is heated above the glass transition temperature (Tg) of PS, and finally, the PS stamp is peeled off, removing from the substrate the micelles that were in contact with the protrusions of the stamp. As a result, patterns of micelles either exactly identical to the original or with much smaller features down to submicrometer were obtained. In a subsequent step, the organic material can be removed and the metal precursor reduced by plasma treatment, resulting in patterns of NPs. This technique, denoted as “μ-contact deprinting”, provides a fast and inexpensive way to obtain hierarchical patterns of NPs on a wide range of substrates. It is demonstrated that it can even be applied on curved surfaces because of the softness of the PS stamp above its T

Hybrid hierarchical patterns of gold nanoparticles and poly(ethylene glycol) microstructures

Hybrid surface micro-patterns composed of topographic structures of polyethylene glycol (PEG)-hydrogels and hierarchical lines of gold nanoparticles (Au NPs) were fabricated on silicon wafers. Micro-sized lines of Au NPs were first obtained on the surface of a silicon wafer via “micro-contact deprinting”, a method recently developed by our group. Topographic micro-patterns of PEG, of both low and high aspect ratio (AR up to 6), were then aligned on the pre-patterned surface via a procedure adapted from the soft lithographic method MIMIC (Micro-Molding in Capillaries), which is denoted as “adhesive embossing”. The result is a complex surface pattern consisting of alternating flat Au NP lines and thick PEG bars. Such patterns provide novel model surfaces for elucidating the interplay between (bio)chemical and physical cues on cell behavior.

In-situ synthesis of gold nanoparticles for multifunctionalization of silk fabrics

A simple in-situ synthesis route for gold nanoparticles (NPs) was developed to realize multifunctions for silk fabrics. The gold NPs were prepared in a heated solution containing white silk fabric samples. The silk fabrics were colored red and brown by the gold NPs because of their localized surface plasmon resonance (LSPR) property. Gold nanospheres on silk were obtained at a low gold content, and gold nanoplates were synthesized as the gold content increased. The silk fabrics treated with gold NPs showed good light fastness. Moreover, the gold NPs endowed silk fabrics with strong antibacterial activity, excellent UV protection property and enhanced thermal conductivity. © 2013 Elsevier Ltd. All rights reserved.

New gold nanostructures for sensor applications: a review

Gold based structures such as nanoparticles (NPs) and nanowires (NWs) have widely been used as building blocks for sensing devices in chemistry and biochemistry fields because of their unusual optical, electrical and mechanical properties. This article gives a detailed review of the new properties and fabrication methods for gold nanostructures, especially gold nanowires (GNWs), and recent developments for their use in optical and electrochemical sensing tools, such as surface enhanced Raman spectroscopy (SERS). © 2014 by the authors; licensee MDPI, Basel, Switzerland.

Boron nitride nanosheets as improved and reusable substrates for gold nanoparticles enabled surface enhanced Raman spectroscopy.

Atomically thin boron nitride (BN) nanosheets have been found to be excellent substrates for noble metal particles enabled surface enhanced Raman spectroscopy (SERS), thanks to their good adsorption of aromatic molecules, high thermal stability and weak Raman scattering. Faceted gold (Au) nanoparticles have been synthesized on BN nanosheets using a simple but controllable and reproducible sputtering and annealing method. The size and density of the Au particles can be controlled by sputtering time, current and annealing temperature etc. Under the same sputtering and annealing conditions, the Au particles on BN of different thicknesses show various sizes because the surface diffusion coefficients of Au depend on the thickness of BN. Intriguingly, decorated with similar morphology and distribution of Au particles, BN nanosheets exhibit better Raman enhancements than silicon substrates as well as bulk BN crystals. Additionally, BN nanosheets show no noticeable SERS signal and hence cause no interference to the Raman signal of the analyte. The Au/BN substrates can be reused by heating in air to remove the adsorbed analyte without loss of SERS enhancement.

In situ synthesis of natural rubber latex-supported gold nanoparticles for flexible SERS substrates

Natural rubber latex (NRL) from Hevea brasiliensis was used as a matrix to synthesize gold nanoparticles (AuNPs), leading to an organic-inorganic hybrid latex of NRL-supported AuNPs (AuNPs@NRL). The in situ and environmentally friendly preparation of AuNPs in an NRL matrix was developed by thermal treatment without using any other reducing agents or stabilizers because natural rubber particles and non-rubber components present in serum can serve as supporters for the synthesized AuNPs. As a result, the nanosized and well-dispersed AuNPs not only are decorated on the surface of natural rubber particles, but also can be found in the serum of NRL. The size of the AuNPs presented in NRL matrix can be controlled by adjusting the concentration of NRL. Furthermore, the flexible surface-enhanced Raman scattering (SERS) substrates made from the AuNPs@NRL through vacuum filtration presented good enhancement of the Raman probe molecule of 4-mercaptopyridine and outstanding SERS reproducibility. The capability of synthesizing the bio-supported nanohybrid latex provides a novel green and simple approach for the fabrication of flexible and effective SERS substrates.

Funtionalized gold nanoparticles for retinoblastoma cancer diagnosis and therapy

 The dissertation reports the synthesis of novel self-therapeutic Surface Enhanced Raman (ST-SERs) active gold nanoparticles. The therapeutic response monitored in the retinoblastoma mice model and elucidated the mechanism of the targeted therapy by biomolecule spectral fingerprints.

Encapsulation of gold nanoparticles with PHB based on coffee ring effect

The hydrodynamic process of ring formation has been utilized to encapsulate gold nanoparticles in the matrix of PHB using an ink jet printing technique. The coffee ring phenomenon on the polymer substrate was elucidated by geometrical evaluation, mathematical formulations and FESEM images.

Sequence-dependent structure/function relationships of catalytic peptide-enabled gold nanoparticles generated under ambient synthetic conditions

Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction data and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.

PEGylated polyethyleneimine-entrapped gold nanoparticles for enhanced and targeted gene delivery applications

Gene therapy, which involves the transfer of nucleic acid into target cells in patients, has become one of the most important and widely explored strategies to treat a variety of diseases, such as cancer, infectious diseases and genetic disorders. Relative to viral vectors that have high immunogenicity, toxicity and oncogenicity, non-viral vectors have gained a lot of interest in recent years. This is largely due to their ability to mimic viral vector features including the capacity to overcome extra- and intra-cellular barriers and to enhance transfection efficiency. Polyethyleneimine (PEI) has been extensively investigated as a non-viral vector. This cationic polymer, which is able to compact nucleic acid through electrostatic interactions and to transport it across the negatively charged cell membranes, has been shown to effectively transfect nucleic acid into different cell lines. Moreover, entrapment of gold nanoparticles (Au NPs) into such an amine-terminated polymer template has been shown to significantly enhance gene transfection efficiency. In this work, a novel non-viral nucleic acid vector system for enhanced and targeted nucleic acid delivery applications was developed. The system was based on the functionalization of PEI with folic acid (FA; for targeted delivery to cancer cells overexpressing FA receptors on their surface) using polyethylene glycol (PEG) as a linker molecule. This was followed by the preparation of PEI-entrapped Au NPs (Au PENPs; for enhancement of transfection efficiency). In the synthesis process, the primary amines of PEI were first partially modified with fluorescein isothiocyanate (FI) using a molar ratio of 1:7. The formed PEI-FI conjugate was then further modified with either PEG or PEGylated FA using a molar ratio of 1:1. This process was finally followed by entrapment of Au NPs into the modified polymers. The resulting conjugates and Au PENPs were characterized by several techniques, namely Nuclear Magnetic Resonance, Dynamic Light Scattering and Ultraviolet-Visible Spectroscopy, to assess their physicochemical properties. In the cell biology studies, the synthesized conjugates and their respective Au PENPs were shown to be non-toxic towards A2780 human ovarian carcinoma cells. The role of these materials as gene delivery agents was lastly evaluated. In the gene delivery studies, the A2780 cells were successfully transfected with plasmid DNA using the different vector systems. However, FA-modification and Au NPs entrapment were not determinant factors for improved transfection efficiency. In the gene silencing studies, on the other hand, the Au PENPs were shown to effectively deliver small interfering RNA, thereby reducing the expression of the B-cell lymphoma 2 protein. Based on these results, we can say that the systems synthesized in this work show potential for enhanced and targeted gene therapy applications.

Electrochemical studies based on local interfacial ph changes of gold nanoparticles immobilized on polystyrene brushes

The electrochemical behavior of polystyrene modified with gold nanoparticle (Au NPs) was investigated in terms of pH-responsive polymer brush. A pH-responsive of modified polymer brush from tethered polystyrene was prepared and used for selective gating transport of anions andcations across the thin-film. An ITO-coated glass electrode was used as substrate and applied to study the switchable permeability of the polymer brush triggered by changes in pH of the aqueous environment. The pH-sensitive behavior of the polymer brush interface has been demonstrated by means of cyclic voltammetry (CV) and Localized Surface Plasmon Resonance (LSPR). CV experiments showed at ph values of 4 and 8 induces swelling and shrinking of the grafted polymer brushes, respectively, and this behavior is fast and reversible. LSPR measurements showed a blue shift of 33 nm in the surface resonance band changes by local pH. The paper brings an easy methodology to fabrication a variety of nanosensors based on the polymer brushes-nanoparticle assemblies. © 2013 by ESG.

Tunable plasmon resonance modes on gold nanoparticles in Er 3 +-doped germanium-tellurite glass

Relative to the Er3 +:gold-nanoparticle (Er3 +:Au-NP) axis, the polarization of the gold nanoparticle can be longitudinal (electric dipole parallel to the Er3 +:Au-NP axis) or transverse (electric dipole perpendicular to the Er3 +:Au-NP axis). For longitudinal polarization, the plasmon resonance modes of gold nanoparticles embedded in Er3 +-doped germanium-tellurite glass are activated using laser lines at 808 and 488 nm in resonance with radiative transitions of Er3 + ions. The gold nanoparticles were grown within the host glass by thermal annealing over various lengths of time, achieving diameters lower than 1.6 nm. The resonance wavelengths, determined theoretically and experimentally, are 770 and 800 nm. The absorption wavelength of nanoparticles was determined by using the Frohlich condition. Gold nanoparticles provide tunable emission resulting in a large enhancement for the 2H11/2 → 4I13/2 (emission at 805 nm) and 4S 3/2 → 4I13/2 (emission at 840 nm) electronic transitions of Er3 + ions; this is associated with the quantum yield of the energy transfer process. The excitation pathways, up-conversion and luminescence spectra of Er3 + ions are described through simplified energy level diagrams. We observed that up-conversion is favored by the excited-state absorption due to the presence of the gold nanoparticles coupled with the Er3 + ions within the glass matrix. © 2013 Elsevier B.V.

Characterization of natural rubber/gold nanoparticles SERS-active substrate

Natural rubber/gold nanoparticles membranes (NR/Au) were studied by ultrasensitive detection and chemical analysis through surface-enhanced Raman scattering and surface-enhanced resonance Raman scattering in our previous work (Cabrera et al., J. Raman Spectrosc. 2012, 43, 474). This article describes the studies of thermal stability and mechanical properties of SERS-active substrate sensors. The composites were prepared using NR membranes obtained by casting the latex solution as an active support (reducing/establishing agents) for the incorporation of colloidal gold nanoparticles (AuNPs). The nanoparticles were synthesized by in situ reduction at different times. The characterization of these sensors was carried out by thermogravimetry, differential scanning calorimetry, scanning electron microscopy (SEM) microscopy, and tensile tests. It is suggested an influence of nanoparticles reduction time on the thermal degradation of NR. There is an increase in thermal stability without changing the chemical properties of the polymer. For the mechanical properties, the tensile rupture was enhanced with the increase in the amount of nanoparticles incorporated in the material. © 2013 Wiley Periodicals, Inc.