Tunable gold nanoparticles shape and size in reductive and structuring media containing protic ionic liquids

Herein, a facile method was developed for preparing high concentration of monodispersed gold nanoparticles (NPs) at room temperature from gold(III) chloride by using different media based on N,N-dimethylformamide or water solutions containing a protic ionic liquid (PIL), namely, the octylammonium formate or the bis(2-ethyl-hexyl)ammonium formate, based on which both PILs were used as redox-active structuring media. The formation of gold NPs in these systems was then characterized using UV-visible spectroscopy, transmission electron microscopy, and dynamic light scattering. From these investigations, it appears that the structure and aggregation pathway of PILs in selected solvents affect strongly the formation, growth, the shape, and the size of gold NPs. In fact, by using this approach, the shape-/ size-controlled gold NPs (branched and spherical) can be generated under mild condition. This approach suggests also a wealth of potential for these designer nanomaterials within the biomedical, materials, and catalysis communities by using designer and safer media based on PILs.

A comparison of gold nanoparticle surface co-functionalization approaches using Polyethylene Glycol (PEG) and the effect on stability, non-specific protein adsorption and internalization

To create clinically useful gold nanoparticle (AuNP) based cancer therapeutics it is necessary to co-functionalize the AuNP surface with a range of moieties; e.g. Polyethylene Glycol (PEG), peptides and drugs. AuNPs can be functionalized by creating either a mixed monolayer by attaching all the moieties directly to the surface using thiol chemistry, or by binding groups to the surface by means of a bifunctional polyethylene glycol (PEG) linker. The linker methodology has the potential to enhance bioavailability and the amount of functional agent that can be attached. While there is a large body of published work using both surface arrangements independently, the impact of attachment methodology on stability, non-specific protein adsorption and cellular uptake is not well understood, with no published studies directly comparing the two most frequently employed approaches. This paper compares the two methodologies by synthesizing and characterizing PEG and Receptor Mediated Endocytosis (RME) peptide co-functionalized AuNPs prepared using both the mixed monolayer and linker approaches. Successful attachment of both PEG and RME peptide using the two methods was confirmed using Dynamic Light Scattering, Fourier Transform Infrared Spectroscopy and gel electrophoresis. It was observed that while the 'as synthesized' citrate capped AuNPs agglomerated under physiological salt conditions, all the mixed monolayer and PEG linker capped samples remained stable at 1M NaCl, and were stable in PBS over extended periods. While it was noted that both functionalization methods inhibited non-specific protein attachment, the mixed monolayer samples did show some changes in gel electrophoresis migration profile after incubation with fetal calf serum. PEG renders the AuNP stable in-vivo however, studies with MDA-MB-231 and MCF 10A cell lines indicated that functionalization with PEG, blocks cellular uptake. It was observed that co-functionalization with RME peptide using both the mixed monolayer and PEG linker methods greatly enhanced cellular internalization compared to PEG capped AuNPs.

Endonuclease Controlled Aggregation of Gold Nanoparticles for the Ultrasensitive Detection of Pathogenic Bacterial DNA

The development of an ultrasensitive biosensor for the low-cost and on-site detection of pathogenic DNA could transform detection capabilities within food safety, environmental monitoring and clinical diagnosis. Herein, we present an innovative approach exploiting endonuclease-controlled aggregation of plasmonic gold nanoparticles (AuNPs) for label-free and ultrasensitive detection of bacterial DNA. The method utilizes RNA-functionalized AuNPs which form DNA-RNA heteroduplex structures through specific hybridization with target DNA. Once formed, the DNA-RNA heteroduplex is susceptible to RNAse H enzymatic cleavage of the RNA probe, allowing the target DNA to liberate and hybridize with another RNA probe. This continuously happens until all of the RNA probes are cleaved, leaving the nanoparticles unprotected and thus aggregated upon exposure to a high electrolytic medium. The assay is ultrasensitive, allowing the detection of target DNA at femtomolar level by simple spectroscopic analysis (40.7 fM and 2.45 fM as measured by UV-vis and dynamic light scattering (DLS), respectively). The target DNA spiked food matrix (chicken meat) is also successfully detected at a concentration of 1.2 pM (by UV-vis) or 18.0 fM (by DLS). In addition to the ultra-high sensitivity, the total analysis time of the assay is less than 3 hours, thus demonstrating its practicality for food analysis.

Brillouin scattering of light by spin waves in ferromagnetic nanorods

We report the investigations of spin wave modes of arrays of Ni and Co nanorods using Brillouin light scattering. We have revealed the significant influence of spin wave modes along the nanorod axis in contrast to infinite magnetic nanowires. Unusual optical properties featuring an inverted Stokes/anti-Stokes asymmetry of the Brillouin scattering spectra have been observed. The spectrum of spin wave modes in the nanorod array has been calculated and compared with the experiment. Experimental observations are explained in terms of a combined numerical-analytical approach taking into account both the low aspect ratio of individual magnetic nanorods and dipolar magnetic coupling between the nanorods in the array. The optical studies of spin-wave modes in nanorod metamaterials with low aspect ratio nanorods have revealed new magnetic and magneto-optical properties compared to continuous magnetic films or infinite magnetic nanowires. Such magnetic artificial materials are important class of active metamaterials needed for prospective data storage and signal processing applications. © 2012 Elsevier B.V.

Release kinetics of oleyl alcohol from a self-lubricating silicone biomaterial

The development of self-lubricating silicone elastomeric biomaterials, prepared using the novel crosslinking agent tetra( oleyloxy) silane and having very low coefficients of friction, has recently been reported. In this study, the in vitro release characteristics of lubricious oleyl alcohol produced during the silicone curing reaction have been quantitatively evaluated for a range of tetra( propoxy) silane/tetra(oleyloxy) silane crosslinker compositions using a novel evaporative light scattering detection method in combination with high performance liquid chromatography. The mechanism of oleyl alcohol release was seen to deviate from a simple, matrix-controlled diffusion process and instead obeyed an anomalous transport mechanism. An explanation for the observed release behaviour has been proposed based on competitive reaction kinetics between the tetra( oleyloxy) silane and tetra( propoxy) silane substituents of the silicone crosslinking agents.

The use of Raman microscopy to determine and localize vitamin E in biological samples

Alpha-tocopherol (aT), the predominant form of vitamin E in mammals, is thought to prevent oxidation of polyunsaturated fatty acids. In the lung, aT is perceived to be accumulated in alveolar type II cells and secreted together with surfactant into the epithelial lining fluid. Conventionally, determination of aT and related compounds requires extraction with organic solvents. This study describes a new method to determine and image the distribution of aT and related compounds within cells and tissue sections using the light-scattering technique of Raman microscopy to enable high spatial as well as spectral resolution. This study compared the nondestructive analysis by Raman microscopy of vitamin E, in particular aT, in biological samples with data obtained using conventional HPLC analysis. Raman spectra were acquired at spatial resolutions of 2-0.8 microm. Multivariate analysis techniques were used for analyses and construction of corresponding maps showing the distribution of aT, alpha-tocopherol quinone (aTQ), and other constituents (hemes, proteins, DNA, and surfactant lipids). A combination of images enabled identification of colocalized constituents (heme/aTQ and aT/surfactant lipids). Our data demonstrate the ability of Raman microscopy to discriminate between different tocopherols and oxidation products in biological specimens without sample destruction. By enabling the visualization of lipid-protein interactions, Raman microscopy offers a novel method of investigating biological characterization of lipid-soluble compounds, including those that may be embedded in biological membranes such as aT.

Raman spectroscopy for the detection of AGEs/ALEs

Raman spectroscopy is a noninvasive, nondestructive tool for capturing multiplexed biochemical information across diverse molecular species including proteins, lipids, DNA, and mineralizations. Based on light scattering from molecules, cells, and tissues, it is possible to detect molecular fingerprints and discriminate between subtly different members of each biochemical class. Raman spectroscopy is ideal for detecting perturbations from the expected molecular structure such as those occurring during senescence and the modification of long-lived proteins by metabolic intermediates as we age. Here, we describe the sample preparation, data acquisition, signal processing, data analysis and interpretation involved in using Raman spectroscopy for detecting age-related protein modifications in complex biological tissues.

Thermodynamic Properties of Mixtures Containing Ionic Liquids. 4. LLE of Binary Mixtures of [C2MIM][NTf2] with Propan-1-ol, Butan-1-ol, and Pentan-1-ol and [C4MIM][NTf2] with Cyclohexanol and 1,2-Hexanediol Including Studies of the Influence of Small Amounts of Water

Experimental data are presented for liquid-liquid equilibria of mixtures of the room-temperature ionic liquid 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide ([C2MIM][NTf2]) with the three alcohols propan-1-ol, butan-1-ol, and pentan-1-ol and for the 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl) imide ([C4MIM][NTf2]) with cyclohexanol and 1,2-hexanediol in the temperature range of 275 K to 345 K at ambient pressure. The synthetic method has been used. Cloud points at a given composition were observed by varying the temperature and using light scattering to detect the phase splitting. In addition, the influence of small amounts of water on the demixing temperatures of binary mixtures of [C2MIM][NTf2] and propan-1-ol, butan-1-ol, and pentan-1-ol was investigated.

Effect of defects on optical phonon Raman spectra in SiC nanorods

Fabricated one-dimensional (1D) materials often have abundant structural defects. Experimental observation and numerical calculation indicate that the broken translation symmetry due to structural defects may play a more important role than the quantum confinement effect in the Raman features of optical phonons in polar semiconductor quantum wires such as SiC nanorods, (C) 1999 Elsevier Science Ltd. All rights reserved.

A new method for non-labeling attomolar detection of diseases based on an individual gold nanorod immunosensor

Herein, we present the use of a single gold nanorod sensor for detection of diseases on an antibody-functionalized surface, based on antibody–antigen interaction and the localized surface plasmon resonance (LSPR) ?max shifts of the resonant Rayleigh light scattering spectra. By replacing the cetyltrimethylammonium bromide (CTAB), a tightly packed self-assembled monolayer of HS(CH2)11(OCH2CH2)6OCH2COOH(OEG6) has been successfully formed on the gold nanorod surface prior to the LSPR sensing, leading to the successful fabrication of individual gold nanorod immunosensors. Using prostate specific antigen (PSA) as a protein biomarker, the lowest concentration experimentally detected was as low as 111 aM, corresponding to a 2.79 nm LSPR ?max shift. These results indicate that the detection platform is very sensitive and outperforms detection limits of commercial tests for PSA so far. Correlatively, its detection limit can be equally compared to the assays based on DNA biobarcodes. This study shows that a gold nanorod has been used as a single nanobiosensor to detect antigens for the first time; and the detection method based on the resonant Rayleigh scattering spectrum of individual gold nanorods enables a simple, label-free detection with ultrahigh sensitivity.

Synthesis and characterization of amphiphilic star copolymers of 2-(dimethylamino) ethyl methacrylate and methyl methacrylate: Effects of architecture and composition

Six amphiphilic star copolymers comprising hydrophilic units of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and hydrophobic units of methyl methacrylate (MMA) were prepared by the sequential group transfer polymerization (GTP) of the two comonomers and ethylene glycol dimethacrylate (EGDMA) cross-linker. Four star-block copolymers of different compositions, one miktoarm star, and one statistical copolymer star were synthesized. The molecular weights (MWs) and MW distributions of all the star copolymers and their linear homopolymer and copolymer precursors were characterized by gel permeation chromatography (GPC), while the compositions of the stars were determined by proton nuclear magnetic resonance (H-1 NMR) spectroscopy. Tetrahydrofuran (THF) solutions of all the star copolymers were characterized by static light scattering to determine the absolute weight-average MW ((M) over bar (w)) and the number of arms of the stars. The R, of the stars ranged between 359,000 and 565,000 g mol(-1), while their number of arms ranged between 39 and 120. The star copolymers were soluble in acidic water at pH 4 giving transparent or slightly opaque solutions, with the exception of the very hydrophobic DMAEMA(10)-b-MMA(30)-star, which gave a very opaque solution. Only the random copolymer star was completely dispersed in neutral water, giving a very opaque solution. The effective pKs of the copolymer stars were determined by hydrogen ion titration and were found to be in the range 6.5-7.6. The pHs of precipitation of the star copolymer solutions/dispersions were found to be between 8.8-10.1, except for the most hydrophobic DMA-EMA(10)-b-MMA(30)-Star, which gave a very opaque solution over the whole pH range. (c) 2006 Elsevier Ltd. All rights reserved.

Synthesis and characterization of star polymers and cross-linked star polymer model networks with cores based on an asymmetric, hydrolyzable dimethacrylate cross-linker

A hydrolyzable dimethacrylate cross-linker, 2-methyl-2,4-pentanediol dimethacrylate (MPDMA), was synhesized by the reaction of 2-methyl-2,4-pentanediol and methacryloyl chloride in the presence of triethylamine. This cross-linker was used to prepare a neat cross-linker network and three cross-linked star polymer model networks (CSPMNs) of methyl methacrylate (MMA), as well as star-shaped polymers of MMA, by group transfer polymerization (GTP). Gel permeation chromatography (GPC) in tetrahydrofuran (THF) confirmed the narrow molecular weight distributions (MWDs) of the linear polymer precursors, and demonstrated the increase in molecular weight (MW) on each successive addition of cross-linker or monomer. Characterization of the star polymers by static light scattering (SLS) in THF showed that star polymers with MPDMA cores bear a relatively small number of arms, between 7 and 35. All star polymers and polymer networks containing the MPDMA cross-linker were hydrolyzed at room temperature in neat trifluoroacetic acid to yield lower-MW products.

Synthesis and characterization of polymer networks and star polymers containing a novel, hydrolyzable acetal-based dimethacrylate cross-linker

An acid-labile dimethaerylate acetal cross-linker,di(methacryloyloxy-l-ethoxy)methane(DMOEM), was synthesized by the reaction of 2-hydroxyethyl methacrylate and paraformaldehyde using p-toluenesulfonic acid and toluene as catalyst and solvent, respectively. Group transfer polymerization was employed to use this cross-linker in the preparation of nine hydrolyzable polymer structures: one neat cross-linker network, one randomly cross-linked network of methyl methacrylate (MMA), and seven star-shaped polymers of MMA. Gel permeation chromatography (GPC) in tetrahydrofuran (THF) confirmed the narrow molecular weight distributions of the linear polymer precursors to the stars and demonstrated the increase in molecular weight upon the addition of cross-linker for the formation of star-shaped polymers. Characterization of the star polymers in THF using static light scattering and GPC showed that the molecular weights and the number of arms of each star polymer increased with an increase in the molar ratio of cross-linker to initiator and with a decrease in the molar ratio of monomer to initiator. The star polymers with DMOEM cores bore a smaller number of arms than those cross-linked with the non-hydrolyzable commercial cross-linker ethylene glycol dimethacrylate due to the bulkier structure of DMOEM. All DMOEM-containing polymer networks and star polymers were completely hydrolyzed within 48 h using hydrochloric acid in THF.

Synthesis and characterization of star polymers and cross-linked star polymer model networks containing a novel, silicon-based, hydrolyzable cross-linker

An acid-labile dimethacrylate cross-linker, dimethyldi(methacryloyloxy-l-ethoxy)silane (DMDMAES), was synthesized by the reaction of 2-hydroxyethyl methacrylate (HEMA) and dichlorodimethylsilane in the presence of triethylamine. Group transfer polymerization (GTP) was employed to use this cross-linker in the preparation of six hydrolyzable polymer structures: one neat cross-linker network, one randomly cross-linked network of methyl methacrylate (MMA), two star-shaped polymers of MMA, and two cross-linked star polymer model networks (CSPMNs) of MMA. A nonhydrolyzable CSPMN of MMA, based on a stable cross-linker, was also synthesized. Gel permeation chromatography (GPC) in tetrahydrofuran (THF) confirmed the narrow molecular weight distributions (MWDs) of the linear polymer precursors and demonstrated the increase in molecular weight (MW) upon each successive addition of cross-linker or monomer. Characterization by static light scattering (SLS) and GPC showed that star polymers with DMDMAES cores bear a relatively small number of arms, around 7. All star polymers and polymer networks were hydrolyzed using hydrochloric acid in THF. While the MWs of the products from the hydrolysis of the star polymers, the neat cross-linker network, and the randomly cross-linked network were as expected, those from the CSPMNs were of a much higher than expected MW, indicating extensive star-star coupling.

Phase Behavior of Reverse Poloxamers and Poloxamines in Water

The phase behavior of two types of poly(ethylene oxide)/poly(propylene oxide) (PEO/PPO) copolymers in aqueous solutions was studied by light scattering, viscometry, and infrared spectroscopy. Both the reverse poloxamer (Pluronic 10R5) and the star type poloxamine (Tetronic 90R4) have practically the same PEO/PPO ratio with their hydrophobic blocks (PPO) located in the outer part. The temperature-composition phase diagrams show that both 10R5 and 90R4 tend to form aggregates in water. Up to four different phases can be detected in the case of Tetronic 90R4 for each temperature: unimers, random networks, micellar networks, and macrophase separation. Viscometric and infrared measurements complemented the results obtained by light scattering and visual inspection.