Label Free Colorimetric Biosensing Using Nanoparticles

In this review article, we discuss a class of biosensors that exploit the change in the colorimetric properties of noble metal nanoparticles in response to biomolecular binding at their surface. Several sensor fabrication techniques as well as sensor configurations are discussed with an emphasis on their strengths and limitations. We conclude by presenting the future prospects and challenges for the successful transition of this technology from the laboratory to a commercial product.     

The response of thermally and optically stimulated luminescence from Al2O3:C to high-energy heavy charged particles

The thermoluminescence (TL) and optically stimulated luminescence (OSL) response of Al₂O₃ dosimeters to high-energy heavy charged particles (HCP) has been studied using the heavy ion medical accelarator at Chiba, Japan. The samples were Al₂O₃ single-crystal chips, of the type usually known as TLD-500, and Luxel^TM dosimeters (Al₂O₃:C powder in plastic) from Landauer Inc. The samples were exposed to ⁴He (150 MeV/u), ¹²C (400 MeV/u), ²⁸Si (490 MeV/u) and ⁵⁶Fe (500 MeV/u) ions, with linear energy transfer values covering the range from 2.26 to 189 keV/μm in water and doses from 1 to 100 mGy (to water). A ⁹⁰Sr/⁹⁰Y beta source, calibrated against a ⁶⁰Co secondary standard, was used for calibration purposes. For OSL, we used both continuous-wave OSL measurements (CW-OSL, using green light stimulation at 525 nm) and pulsed OSL measurements (POSL, using 532 nm stimulation from a Nd:YAG Q-switched laser). The efficiencies (η_HCP,γ) of the different HCPs at producing OSL or TL were observed to depend not only upon the linear energy transfer (LET) of the HCP, but also upon the sample type (single crystal chip or Luxel^TM) and the luminescence method used to define the signal—i.e. TL, CW-OSL initial intensity, CW-OSL total area, or POSL. Observed changes in shape of the decay curve lead to potential methods for extracting LET information of unknown radiation fields. A discussion of the results is given, including the potential use of OSL from Al₂O₃ in the areas of space radiation dosimetry and radiation oncology.     

Preparation of Ultrafine Colloidal Gold Particles using a Bioactive Molecule

Synthesis of nanometer-sized particles with new physical properties is an area of tremendous interest. In metal particles, the changes in size modify the electron density in the particles, which shifts the plasmon band. The most significant size effects occur when the particles are ultrafine (size is <10 nm). Thus the synthesis of ultrafine metal particles is enormously important to exploit their unique and selective application. Here we report a novel method for the synthesis of ultrafine gold particles in the size range of 0.5–3 nm using dopamine hydrochloride (dhc), an important neurotransmitter. This is the first time where such an important bioactive molecule like dhc has been used as a reagent for the transformation of Au(III) to Au(0). The synthesis is carried out, for the first time, either in simple aqueous or in a nonionic micellar (for example Triton X-100 (TX-100)) medium. The gold sol has a beautiful yellow–brown color showing _max at 470 nm. The appearance of the absorption peak at substantially shorter wavelength (usually gold sol absorbs at 520 nm) indicates that the particles are very small. The method discussed here is very simple, reproducible and does not involve any reagent, which contains 'P' or 'S' atoms. Also in this case no polymer or dendrimer or thiol-related stabilizer is used. The effects of different parameters (such as the presence or absence of O₂, temperature, TX-100 concentration and dhc concentration) on the formation of ultrafine gold particles are discussed. The effects of 3-mercapto propionic acid and pyridine on the ultrafine gold sol are also studied and compared with those on photochemically prepared gold sol. It is observed that 3-mercapto propionic acid dampens the plasmon absorption at 470 nm of ultrafine gold particles. Pyridine, on the other hand, has no effect on the particles.     

Electronic and vibrational properties of fluorenone in the channels of zeolite L

Fluorenone (C13H8O) was inserted into the channels of zeolite L by using gas-phase adsorption. The size, structure, and stability of fluorenone are well suited for studying host-guest interactions. The Fourier transform IR, Raman, luminescence, and excitation spectra, in addition to thermal analysis data, of fluorenone in solution and fluorenone/zeolite L are reported. Normal coordinate analysis of fluorenone was performed, based on which IR and Raman bands were assigned, and an experimental force field was determined. The vibrational spectra can be used for nondestructive quantitative analysis by comparing a characteristic dye band with a zeolite band that has been chosen as the internal standard. Molecular orbital calculations were performed to gain a better understanding of the electronic structure of the system and to support the interpretation of the electronic absorption and luminescence spectra. Fluorenone shows unusual luminescence behavior in that it emits from two states. The relative intensity of these two bands depends strongly on the environment and changes unexpectedly in response to temperature. In fluorenone/zeolite L, the intensity of the 300 nm band (lifetime 9 micros) increases with decreasing temperature, while the opposite is true for the 400 nm band (lifetime 115 micros). A model of the host-guest interaction is derived from the experimental results and calculations: the dye molecule sits close to the channel walls with the carbonyl group pointing to an Al3+ site of the zeolite framework. A secondary interaction was observed between the fluorenone's aromatic ring and the zeolite's charge-compensating cations.     

Role of quantum-sized effects on the cathodic photocorrosion of ZnO nanoparticles in ethanol

Cathodic photocorrosion occurs upon stationary photoirradiation of ethanolic ZnO sols. The photocorrosion rate increases with decreasing particle size. This effect due to the appearance of quantum-sized effects in ZnO nanocrystals results from an increase in the reduction potential of the semiconductor upon irradiation, which may exceed the Fermi level for cathodic decomposition of zinc oxide nanoparticles.Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol.40, No.6, pp. 363–367, November–December, 2004.     

Saturated absorption and nonlinear refraction of silicate glasses doped with silver nanoparticles at 532 nm

The nonlinear optical characteristics of silicate glasses doped with silver nanoparticles are investigated by Z-scan technique using second harmonic radiation of picosecond Nd:YAG laser (=532 nm, =55 ps). The real and imaginary parts of third-order nonlinear susceptibility of silver-contained glasses were measured. It was found that the sign of Im ⁽³⁾was negative due to saturated absorption and the sign of Re ⁽³⁾ was changed from negative (self-defocusing) to positive (self-focusing) with growth of laser radiation intensity. The mechanisms responsible for saturated absorption and nonlinear refraction are discussed.     

Monosized cationic nanoparticles prepared by emulsifer-free emulsion polymerization

Monosized poly(styrene/N-[3-(dimethylamino)propyl]methacrylamide/poly(ethylene glycol) ethyl ether methacrylate) [poly(St/PEG-EEM/DMAPM)] cationic nanoparticles were synthesized by emulsifier-free emulsion polymerization conducted in the presence of a cationic initiator, 2,2-azobis(2-methylpropionamidine) dihydrochloride (APDH or V-50). Particle sizes and surface charge densities were measured with a Zeta Sizer. The structure of the terpolymers was determined by Fourier transform IR and ¹H NMR spectroscopies. The amounts of the main monomer (St), cationic comonomer (DMAPM), stabilizer (PEG-EEM), and initiator (APDH), and the water-to-monomer phase ratio were all effective on both the average size and the surface charge of the nanoparicles. The average particle size was in the range 75–400 nm depending on the recipe applied; it decreased on increasing the amount of DMAP or PEG-EEM or the water-to-monomer phase ratio in the feed, while it increased with increasing St or APDH content. These nanoparticles were quite monodisperse with a polydispersity index of 1.008–1.14.     

Calculation of the Loss Coefficient of Amplified Luminescence in the Active Layer of a Laser Diode

A method to calculate the loss coefficient of amplified luminescence _loss ^lum in the active layer of a laser diode on the basis of radiation transfer equations and the balance between emission, amplification, and absorption of spontaneous radiation is suggested. The values of _loss ^lum and also of the density of fluxes of amplified luminescence have been determined in one- and two-dimensional approximations for laser diodes based on GaAs, GaN, and ZnSe compounds with different configurations of resonators.     

Luminescence of Molecules with Internal Charge Transfer upon Longwave Excitation

We have studied the spectral properties of luminescence of laurdan molecules in glycerin upon excitation at the red edge of the absorption band at different temperatures. The most significant red-wave shift of the spectra (10 nm) for the longwave band of dual fluorescence is observed depending on the excitation wavelength at a low temperature of 260 K when a solvent forms a fairly rigid matrix. At the same time, at increased temperatures of up to 370 K a small bathochromic shift and a change in the shape of the luminescence bands are also recorded reliably. Changes in the excitation spectra were observed when luminescence was recorded in the bands of the LE- and CT states. The difference spectrum responsible for the additional absorption that does not make a contribution to the longwave luminescence component has been isolated. The decay kinetics of both luminescence components have been measured and their expansions in decay constants have been analyzed. The experimental dependences obtained point to the complex mechanism of inhomogeneous broadening of spectra.