Synthesis and characterization of surface-enhanced Raman-scattered gold nanoparticles

In this paper, we report a simple, rapid, and robust method to synthesize surface-enhanced Raman-scattered gold nanoparticles (GNPs) based on green chemistry. Vitis vinifera L. extract was used to synthesize noncytotoxic Raman-active GNPs. These GNPs were characterized by ultraviolet-visible spectroscopy, dynamic light-scattering, Fourier-transform infrared (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. The characteristic surface plasmon-resonance band at ~528 nm is indicative of spherical particles, and this was confirmed by TEM. The N–H and C–O stretches in FTIR spectroscopy indicated the presence of protein molecules. The predominant XRD plane at (111) and (200) indicated the crystalline nature and purity of GNPs. GNPs were stable in the buffers used for biological studies, and exhibited no cytotoxicity in noncancerous MIO-M1 (Müller glial) and MDA-MB-453 (breast cancer) cell lines. The GNPs exhibited Raman spectral peaks at 570, 788, and 1,102 cm-1. These new GNPs have potential applications in cancer diagnosis, therapy, and ultrasensitive biomarker detection.

Synthesis and preliminary investigations into norbornane-based amphiphiles and their self-assembly

A range of norbornane based amphiphiles, which possess a rigid 'kink' in the centre of amphiphiles, were accessed via a concise four step synthesis. The self-assembly properties of these novel compounds were then investigated and the critical aggregation concentration (CAC), hydrodynamic diameter (DH) by dynamic light scattering (DLS) and their morphology by cryogenic transmission electron microscopy (cryoTEM) and negatively stained transmission electron microscopy (TEM) were determined. These compounds while possessing similar CAC values (50-70 μM) exhibited a wide variety of particle size (60-140 nm) and morphologies, including vesicles, cigar-shaped aggregates and rod-like micelles. Considering the similarities in molecular structure we have proposed that the unique nature of the molecular 'kink' is affecting molecular assembly in which subtle changes in molecular structure have large ramifications on aggregate size and morphology.

Self-assembled multimicellar vesicles via complexation of a rigid conjugated polymer with an amphiphilic block copolymer

A viable method of encapsulating block copolymer micelles inside vesicles using a conjugated polymer is reported in this study. Self-assembly and complexation between an amphiphilic block copolymer poly(methyl methacrylate)-b-poly(acrylic acid) (PMMA-b-PAA) and a rod-like conjugated polymer polyaniline (PANI) in aqueous solution were studied using transmission electron microscopy, atomic force microscopy and dynamic light scattering. The complexation and morphology transformation were driven by electrostatic interaction between PANI and the PAA block of the block copolymer. Addition of PANI to PMMA-b-PAA induced the morphology transformation from micelles to irregular vesicles through vesicles, thick-walled vesicles (TWVs) and multimicellar vesicles (MMVs). Among the observed morphologies, MMVs were observed for the first time. Morphology transformation was studied as a function of aniline/acrylic acid molar ratio ([ANI]/[AA]). Micelles were observed for the pure block copolymer, while vesicles and TWVs were observed at [ANI]/[AA] = 0.1 and 0.3, respectively. MMVs were observed at [ANI]/[AA] = 0.5 and irregular vesicles were observed for molar ratios at 0.7 and above. Clearly, a conjugated polymer like polyaniline can induce a morphology transformation even at its lower concentrations and produce complex morphologies.

Large compound vesicles from amphiphilic block copolymer/rigid-rod conjugated polymer complexes

Morphology evolution in complexes of amphiphilic block copolymers poly(styrene)-b-poly(acrylic acid) (PS-b-PAA) and poly(styrene)-b-poly(ethylene oxide) (PS-b-PEO) in the presence of polyaniline (PANI) in aqueous solution is reported. Transmission electron microscopy, atomic force microscopy, and dynamic light scattering techniques were used to study the morphologies at various PANI contents [aniline]/[acrylic acid] ([ANI]/[AA]) ranging from 0.1 to 0.7. The interpolyelectrolyte complex formed between PAA and PANI plays a key role in the morphology transformation. Spherical micelles formed from pure block copolymers were transformed into large compound vesicles upon increasing PANI concentration due to internal block copolymer segregation. In addition to varying PANI content, the kinetic pathway of nanoparticle formation was controlled through different water addition methods and was critical in the formation of multigeometry nanoparticles.

Milled non-mulberry silk fibroin microparticles as biomaterial for biomedical applications

Silk fibroin has been widely employed in various forms as biomaterials for biomedical applications due to its superb biocompatibility and tunable degradation and mechanical properties. Herein, silk fibroin microparticles of non-mulberry silkworm species (Antheraea assamensis, Antheraea mylitta and Philosamia ricini) were fabricated via a top-down approach using a combination of wet-milling and spray drying techniques. Microparticles of mulberry silkworm (Bombyx mori) were also utilized for comparative studies. The fabricated microparticles were physico-chemically characterized for size, stability, morphology, chemical composition and thermal properties. The silk fibroin microparticles of all species were porous (∼5μm in size) and showed nearly spherical morphology with rough surface as revealed from dynamic light scattering and microscopic studies. Non-mulberry silk microparticles maintained the typical silk-II structure with β-sheet secondary conformation with higher thermal stability. Additionally, non-mulberry silk fibroin microparticles supported enhanced cell adhesion, spreading and viability of mouse fibroblasts than mulberry silk fibroin microparticles (p<0.001) as evidenced from fluorescence microscopy and cytotoxicity studies. Furthermore, in vitro drug release from the microparticles showed a significantly sustained release over 3 weeks. Taken together, this study demonstrates promising attributes of non-mulberry silk fibroin microparticles as a potential drug delivery vehicle/micro carrier for diverse biomedical applications.

EpCAM aptamer mediated cancer cell specific delivery of EpCAM siRNA using polymeric nanocomplex

BACKGROUND: Epithelial cell adhesion molecule (EpCAM) is overexpressed in solid tumors and regarded as a putative cancer stem cell marker. Here, we report that employing EpCAM aptamer (EpApt) and EpCAM siRNA (SiEp) dual approach, for the targeted delivery of siRNA to EpCAM positive cancer cells, efficiently inhibits cancer cell proliferation. RESULTS: Targeted delivery of siRNA using polyethyleneimine is one of the efficient methods for gene delivery, and thus, we developed a novel aptamer-PEI-siRNA nanocomplex for EpCAM targeting. PEI nanocomplex synthesized with EpCAM aptamer (EpApt) and EpCAM siRNA (SiEp) showed 198 nm diameter sized particles by dynamic light scattering, spherical shaped particles, of 151 ± 11 nm size by TEM. The surface charge of the nanoparticles was -30.0 mV using zeta potential measurements. Gel retardation assay confirmed the PEI-EpApt-SiEp nanoparticles formation. The difference in size observed by DLS and TEM could be due to coating of aptamer and siRNA on PEI nanocore. Flow cytometry analysis revealed that PEI-EpApt-SiEp has superior binding to cancer cells compared to EpApt or scramble aptamer (ScrApt) or PEI-ScrApt-SiEp. PEI-EpApt-SiEp downregulated EpCAM and inhibited selectively the cell proliferation of MCF-7 and WERI-Rb1 cells. CONCLUSIONS: The PEI nanocomplex fabricated with EpApt and siEp was able to target EpCAM tumor cells, deliver the siRNA and silence the target gene. This nanocomplex exhibited decreased cell proliferation than the scrambled aptamer loaded nanocomplex in the EpCAM expressing cancer cells and may have potential for EpCAM targeting in vivo.

Flower like micellar assemblies in poly(styrene)-block-poly(4-vinylpyridine)/poly(acrylic acid) complexes

The formation of rare flower like micelles in poly(styrene)-block-poly(4-vinyl pyridine)/poly(acrylic acid) (PS-b-P4VP/PAA) diblock copolymer/homopolymer complexes is reported. The self-assembly as well as the morphological changes in the complexes were induced by the addition of a high molecular weight PAA/ethanol solution into the PS-b-P4VP solution in dimethyl formamide followed by dialyses. The composition-dependent micelles were varying in size and shape with increase in PAA concentration in solution. The complex aggregates in solution were characterized by dynamic light scattering (DLS) whereas morphologies in the solid complexes were observed using transmission electron microscopy (TEM). Flower like micelles are formed in complexes at 20 wt% PAA concentration followed by 'spikey' micellar assemblies at 40 wt% PAA. The size of the micelles was found to be increased upon the addition of PAA into the block copolymer solution. Infrared studies revealed the intermolecular hydrogen bonding interactions between the complementary binding sites on PAA and the P4VP block of the block copolymer. Finally, a model was proposed to explain the self-assembly and morphological transitions in these complexes based on the experimental results obtained.

Improvement of light harvesting and device performance of dye-sensitized solar cells using rod-like nanocrystal TiO2 overlay coating on TiO2 nanoparticle working electrode

Novel TiO2 single crystalline nanorods were synthesized by electrospinning and hydrothermal treatment. The role of the TiO2 nanorods on TiO2 nanoparticle electrode in improvement of light harvesting and photovoltaic properties of dye-sensitized solar cells (DSSCs) was examined. Although the TiO2 nanorods had lower dye loading than TiO2 nanoparticle, they showed higher light utilization behaviour. Electron transfer in TiO2 nanorods received less resistance than that in TiO2 nanoparticle aggregation. By just applying a thin layer of TiO2 nanorods on TiO2 nanoparticle working electrode, the DSSC device light harvesting ability and energy conversion efficiency were improved significantly. The thickness of the nanorod layer in the working electrode played an important role in determining the photovoltaic property of DSSCs. An energy conversion efficiency as high as 6.6% was found on a DSSC device with the working electrode consisting of a 12 μm think TiO2 nanoparticle layer covered with 3 μm thick TiO2 nanorods. The results obtained from this study may benefit further design of highly efficient DSSCs.