Environmentally friendly synthesis of highly monodisperse biocompatible gold nanoparticles with urchin-like shape

We report a facile and environmentally friendly strategy for high-yield synthesis of highly monodisperse gold nanoparticles with urchin-like shape. A simple protein, gelatin, was first used for the control over shape and orientation of the gold nanoparticles. These nanoparticles, ready to use for biological systems, are promising in the optical imaging-based disease diagnostics and therapy because of their tunable surface plasmon resonance (SPR) and excellent surface-enhanced Raman scattering (SERS) activity.

Ethanol-induced formation of silver nanoparticle aggregates for highly active SERS substrates and application in DNA detection

A controllable silver nanoparticle aggregate system has been synthesized by adding different amounts of ethanol to cetyltrimethylammonium bromide (CTAB) capped silver nanoparticles (Ag-nps), which could be used as highly efficient surface-enhanced Raman scattering (SERS) active substrates. This ethanol-induced aggregation can be attributed to preferential dissolution of CTAB into ethanol, which leads a partial removal of the protective CTAB layer on Ag-nps. The optical and morphological properties of these aggregates under various volumes of ethanol were explored via UV-vis spectroscopy and atomic force microscopy.

Fabrication, characterization, and application in surface-enhanced Raman spectrum of assembled type-I collagen-silver nanoparticle multilayered films

In this paper, we report a facile method for the fabrication of type-I collagen-silver nanoparticles (Ag NPs) multilayered films by utilizing type-I collagen as a medium. These samples were characterized by UV-vis spectra photometer, atomic force microscopy, scanning electron microscopy, and Fourier transform IR spectrum. Experimental results show that collagen molecules serve as effective templates to assemble Ag NPs into multilayer films. These samples exhibit high surface-enhanced Raman scattering (SERS) enhancement abilities.

Photochemical synthesis and self-assembly of gold nanoparticles

Colloidal gold was prepared by UV light irradiation of the mixture of HAuCl4 aqueous solution and poly(vinyl pyrrolidone) (PVP) ethanol solution in the presence of silver ions. The resulting sheet-like nanoparticles were found to self-assemble into nanoflowers by a centrifuging process. The results of control experiments reflected that only suitable size sheet-like nanoparticles could assemble into the flower-like structures. The presence of Ag ions and PVP are essential for the formation process of nanoflowers.

Gold nanoparticle probes

Depending on their size, shape. degree of aggregation and nature of the protecting organic shells on their surface, gold nanoparticles (AuNPs) can appear red, blue and other colors and emit bright resonance light scattering of various wavelengths. Because of this unique optical property. AuNPs have been extensively explored as probes for sensing/imaging a wide range of analytes/targets, such as heavy metallic cations, nucleic acids, proteins, cells, etc. Since their initial discovery, novel synthetic methods have led to precise control over particle size, shape and stability, thus allowing the modification of a wide variety of ligands on the AuNP surfaces to meet different experimental conditions. This review discusses the synthesis and applications of functionalized AuNPs in chemical sensing and imaging.

Large-scale, rapid synthesis and application in surface-enhanced Raman spectroscopy of sub-micrometer polyhedral gold nanocrystals

Macromolecule-protected sub-micrometer polyhedral gold nanocrystals have been facilely prepared by heating an aqueous solution containing poly (N-vinyl-2-pyrrolidone) (PVP) and HAuCl4 without adding other reducing agents. Scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX), ultraviolet-visible-near-infrared spectroscopy (UV-vis-NIR), and x-ray diffraction (XRD) were employed to characterize the obtained polyhedral gold nanocrystals. It is found that the 10:1 molar ratio of PVP to gold is a key factor for obtaining quasi-monodisperse polyhedral gold nanocrystals. Furthermore, the application of polyhedral gold nanocrystals in surface-enhanced Raman scattering (SERS) was investigated by using 4-aminothiophenol (4-ATP) as a probe molecule. The results indicated that the sub-micrometer polyhedral gold nanocrystals modified on the ITO substrate exhibited higher SERS activity compared to the traditional gold nanoparticle modified film. The enhancement factor (EF) on polyhedral gold nanocrystals was about six times larger than that obtained on aggregated gold nanoparticles (similar to 25 nm).

Assembly process of CuHCF/MPA multilayers on gold nanoparticles modified electrode and characterization by electrochemical SPR

Gold nanoparticles were deposited onto 2-mercaptoethylamine (MEA)-assembled planar gold thin film to construct gold nanoparticles modified electrode by virtue of a solution-based self-assembly strategy. Subsequently, 3-mercaptopropionic acid (MPA)-bridged copper hexacyanoferrate (CuHCF) multilayers were constructed on the as-prepared gold nanoparticles modified electrode. The resulted multilayer nanostructures were investigated by electrochemical surface plasmon resonance (EC-SPR) and atomic force microscopy (AFM) with primary emphasis upon the effect of the gold nanoparticles on the MPA/CuHCF multilayers growth and their surface morphology. Compared with the multilayer system on a planar gold electrode, the different electrochemical and optical properties might result from higher curvature effect and extraordinary surface-to-volume ratio characteristic of gold nanoparticles and the nanoparticle-selective growth of CuHCF. A dendrimer-like assembly process was proposed to explain the experiment results. This new motif of multilayer on the gold nanoparticles modified electrode was different from that of on a planar gold electrode, indicating a potential application of EC-SPR technique in the study of nanocomposite materials.

Electrochemical and Raman studies of the biointeraction between Escherichia coli and mannose in polydiacetylene derivative supported on the self-assembled monolayers of octadecanethiol on a gold electrode

Here, we describe a new method to study the biointeraction between Escherichia coli and mannose by using supramolecular assemblies composed of polydiacetylene supported on the self-assembled monolayer of octadecanethiol on a gold electrode. These prepared bilayer materials simply are an excellent protosystem to study a range of important sensor-related issues. The experimental results from UV-vis spectroscopy, resonance Raman spectroscopy, and electrochemistry confirm that the specific interactions between E. coli and mannose can cause conformational changes of the polydiacetylene backbone rather than simple nonspecific adsorption. Moreover, the direct electrochemical detection by polydiacetylene supramolecular assemblies not only opens a new path for the use of these membranes in the area of biosensor development but also offers new possibilities for diagnostic applications and screening for binding ligands.

Photoelectrochemical reduction of CO2 mediated with methylviologen at roughened silver electrodes

The photoelectrocatalytic effect for the reduction of CO2 mediated with methylviologen (MV) was studied at mercury, polished silver and roughened silver electrodes using electrochemical and surface-enhanced Raman scattering (SERS) techniques. A large photoelectrocatalytic effect for the reduction of CO2 in the presence of MV was observed at the roughened silver electrode, whereas there was only a very small photoelectrocatalytic current at a more negative potential on mercury and polished silver electrodes. The SERS spectra of MV in the presence and absence of CO2, along with the electrochemical results, demonstrate that the surface adsorbed complexes, MV+ -Ag and MV0-Ag, played a role as the mediator for photoinduced electron transfer to CO2 in the solution. The results also suggest that the surface plasmon resonance of the nanoscale silver particle contributes to the overall photoelectrocatalytic effect on a roughened silver electrode.

Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified class slide: A strategy for SPR substrates

The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.

Hollow core photonic crystal fibre as a viscosity and Raman sensor

This PhD thesis investigates the application of hollow core photonic crystal fibre for use as an optical fibre nano litre liquid sensor. The use of hollow core photonic crystal fibre for optical fibre sensing is influenced by the vast wealth of knowledge, and years of research that has been conducted for optical waveguides. Hollow core photonic crystal fibres have the potential for use as a simple, rapid and continuous sensor for a wide range of applications. In this thesis, the velocity of a liquid flowing through the core of the fibre (driven by capillary forces) is used for the determination of the viscosity of a liquid. The structure of the hollow core photonic crystal fibre is harnessed to collect Raman scatter from the sample liquid. These two methods are integrated to investigate the range of applications the hollow core photonic crystal fibre can be utilised for as an optical liquid sensor. Understanding the guidance properties of hollow core photonic crystal fibre is forefront in dynamically monitoring the liquid filling. When liquid is inserted fully or selectively to the capillaries, the propagation properties change from photonic bandgap guidance when empty, to index guidance when the core only is filled and finally to a shifted photonic bandgap effect, when the capillaries are fully filled. The alterations to the guidance are exploited for all viscosity and Raman scattering measurements. The concept of the optical fibre viscosity sensor was tested for a wide range of samples, from aqueous solutions of propan-1-ol to solutions of mono-saccharides in phosphate buffer saline. The samples chosen to test the concept were selected after careful consideration of the importance of the liquid in medical and industrial applications. The Raman scattering of a wide range of biological important fluids, such as creatinine, glucose and lactate were investigated, some for the first time with hollow core photonic crystal fibre.

Inline holographic coherent anti-Stokes Raman microscopy.

We demonstrate a simple approach for inline holographic coherent anti-Stokes Raman scattering (CARS) microscopy, in which a layer of uniform nonlinear medium is placed in front of a specimen to be imaged. The reference wave created by four-wave mixing in the nonlinear medium can interfere with the CARS signal generated in the specimen to result in an inline hologram. We experimentally and theoretically investigate the inline CARS holography and show that it has chemical selectivity and can allow for three-dimensional imaging.

IR/Raman spectroscopy and DFT calculations of cyclic di-amino acid peptides. Part III: comparison of solid state and solution structures of cyclo(L-Ser-L-Ser)

B3-LYP/cc-pVDZ calculations of the gas-phase structure and vibrational spectra of the isolated molecule cyclo(L-Ser-L-Ser), a cyclic di-amino acid peptide (CDAP), were carried out by assuming C-2 symmetry. It is predicted that the minimum-energy structure is a boat conformation for the diketopiperazine (DKP) ring with both L-Beryl side chains being folded slightly above the ring. An additional structure of higher energy (15.16 kJ mol(-1)) has been calculated for a DKP ring with a planar geometry, although in this case two fundamental vibrations have been calculated with imaginary wavenumbers. The reported X-ray crystallographic structure of cyclo(L-Ser-L-Ser), shows that the DKP ring displays a near-planar conformation, with both the two L-Beryl side chains being folded above the ring. It is hypothesized that the crystal packing forces constrain the DKP ring in a planar conformation and it is probable that the lower energy boat conformation may prevail in the aqueous environment. Raman scattering and Fourier-transform infrared (FT-IR) spectra of solid state and aqueous solution samples of cyclo(L-Ser-L-Ser) are reported and discussed. Vibrational band assignments have been made on the basis of comparisons with the calculated vibrational spectra and band wavenumber shifts upon deuteration of labile protons. The experimental Raman and IR results for solid-state samples show characteristic amide I vibrations which are split (Raman:1661 and 1687 cm(-1), IR:1666 and 1680 cm(-1)), possibly due to interactions between molecules in a crystallographic unit cell. The cis amide I band is differentiated by its deuterium shift of ~ 30 cm(-1), which is larger than that previously reported for trans amide I deuterium shifts. A cis amide II mode has been assigned to a Raman band located at 1520 cm(-1). The occurrence of this cis amide II mode at a wavenumber above 1500 cm(-1) concurs with results of previously examined CDAP molecules with low molecular weight substituents on the C-alpha atoms, and is also indicative of a relatively unstrained DKP ring.

Quantitative surface-enhanced Raman spectroscopy

The purpose of this tutorial review is to show how surface-enhanced Raman (SERS) and resonance Raman (SERRS) spectroscopy have evolved to the stage where they can be used as a quantitative analytical technique. SER(R)S has enormous potential for a range of applications where high sensitivity needs to be combined with good discrimination between molecular targets, particularly since low cost, compact spectrometers can read the high signal levels that SER(R)S typically provides. These advantages over conventional Raman measurements come at the cost of increased complexity and this review discusses the factors that need to be controlled to generate stable and reproducible SER(R)S calibrations.

Disposable, stable media for reproducible surface-enhanced Raman spectroscopy

Large numbers of identical and stable SE(R)RS [surface-enhanced (resonance) Raman]-active media, which are convenient to handle and manipulate but sufficiently inexpensive that they can be used once and then discarded, have been prepared by isolating nanoparticles from Ag and Au sols in hydrophilic polymer gels. The preparation simply involves mixing a suitable polymer with the sol to give a viscous suspension that can be coated onto a substrate and dried to form a hard translucent film. The films remain inactive until they are treated with aqueous analyte solution, which causes the film to swell and brings the analyte into contact with the active metal particles. The swollen films give strong SERS spectra which are effectively identical to those obtained from simple sols. The advantage of this method is that the dried polymers can be stored indefinitely before use and that they give a high degree of spectral reproducibility.