Gold and silver nanoparticles in sensing and imaging: sensitivity of plasmon response to size, shape, and metal composition

Plasmonic metal nanoparticles have great potential for chemical and biological sensor applications, due to their sensitive spectral response to the local environment of the nanoparticle surface and ease of monitoring the light signal due to their strong scattering or absorption. In this work, we investigated the dependence of the sensitivity of the surface plasmon resonance (frequency and bandwidth) response to changes in their surrounding environment and the relative contribution of optical scattering to the total extinction, on the size and shape of nanorods and the type of metal, that is, Au vs Ag. Theoretical consideration on the surface plasmon resonance condition revealed that the spectral sensitivity, defined as the relative shift in resonance wavelength with respect to the refractive index change of surrounding materials, has two controlling factors: first the bulk plasma wavelength, a property dependent on the metal type, and second on the aspect ratio of the nanorods which is a geometrical parameter. It is found that the sensitivity is linearly proportional to both these factors. To quantitatively examine the dependence of the spectral sensitivity on the nanorod metal composition and the aspect ratio, the discrete dipole approximation method was used for the calculation of optical spectra of Ag-Au alloy metal nanorods as a function of Ag concentration. It is observed that the sensitivity does not depend on the type of the metal but depends largely on the aspect ratio of nanorods. The direct dependence of the sensitivity on the aspect ratio becomes more prominent as the size of nanorods becomes larger. However, the use of larger nanoparticles may induce an excessive broadening of the resonance spectrum due to an increase in the contribution of multipolar excitations. This restricts the sensing resolution. The insensitivity of the plasmon response to the metal composition is attributable to the fact that the bulk plasma frequency of the metal, which determines the spectral dispersion of the real dielectric function of metals and the surface plasmon resonance condition, has a similar value for the noble metals. On the other hand, nanorods with higher Ag concentration show a great enhancement in magnitude and sharpness of the plasmon resonance band, which gives better sensing resolution despite similar plasmon response. Furthermore, Ag nanorods have an additional advantage as better scatterers compared with Au nanorods of the same size.     

Rotenoid and isoflavone metabolites from an antioxidant seed extract of Dalbergia lanceolaria subsp. paniculata (roxb.) thoth

Abstract

A new rotenoid named 12-O-methylrotenolol along with five known rotenoid and isoflavone metabolites were isolated from the seeds of Dalbergia lanceolaria subsp. paniculata, collected from Egypt. The structures of these compounds were identified by physical and spectroscopic data measurements ([α]_D, UV, 1D- and 2D-NMR and MS). The methanol extract of the seeds exhibited strong antioxidant activity with IC₅₀ value 0.7?µg/µl against DPPH radical, in respect to quercetin as antioxidant reference (IC₅₀ 1.5?μM), while the tested compounds from this extract showed weak activities with IC₅₀ values ranged from 19.6 to 33.0?µM.     

Immobilization of Keggin and Preyssler tungsten heteropolyacids on various functionalized silica

The Keggin and Preyssler tungsten heteropolyacids, H3PW12O40 and H15P5W30O110, have been immobilized on the inner surface of mesoporous MCM-41, fume silica and silica-gel by means of chemical bonding to aminosilane groups. The materials were characterized by FT-IR spectroscopy, low-angle XRD and BET surface area analysis. The tendencies of heteropolyacids adsorption in solution on functionalized silicas have been investigated by UV-vis. Among the functionalized silica materials, MCM-41 showed the largest amine to silica and the least heteropolyacid to silica ratios. The BET surface area revealed that in all three cases the surface area decreased after grafting amine group and anchoring of the HPAs clusters. Low-angle XRD analysis showed that by introducing HPA into functionalized MCM-41 the intensity of the main reflection decreased significantly.     

Syntheses and crystal structures of two new coordination polymers of Cd(II) using organic spacer and inorganic-bridging ligands

Two new cadmium (II) complexes [Cd(hmt)(dca)₂] _n (1) and [Cd₃(hmt)₂(SeCN)₆(H₂O)₂] _n (2) (hmt=hexamethylenetetramine, dca=dicyanamide) have been synthesized and characterized by X-ray single-crystal analysis. The complex 1 is a 2D rectangular grid of octahedral cadmium (II) with CdN₆ chromophore where cadmium centers are doubly bridged by dicyanamide and hmt along a-axis, which are interlinked by dicyanamide running along c-axis. Whereas, complex 2 is a 1D chain of octahedral cadmium (II) with a three-leg ladder topology running along a-axis. The Cd(II) centers are doubly bridged through SeCN (infinite rail) along a-axis and singly bridged by hmt (two-step rung) along c-axis, having cadmium centers with CdSe₂N₃O and CdSe₂N₄ chromophores. The adjacent chains through H-bonding between coordinated water and hmt, and SeSe interaction are extended to 2D supramolecular architecture.     

Characterization and High Level Expression of Acidic Endoglucanase in Pichia pastoris

Bioconversion of cellulosic material into glucose needs cellulase enzymes. One of the most important organisms that produces cellulases is Trichoderma reesei, whose cellulose enzymes are probably the most widely used in the industry. However, these enzymes are not stable enough at high pH and temperatures. The optimized synthetic endoglucanase II gene with Pichia pastoris codon preferences was secretary expressed in P. pastoris. Recombinant enzyme characterization showed maximum activity at pH 4.8 and temperature 75 °C, and it demonstrated increasing thermal stability in high temperature. The enzyme maintained its activity in a wide pH range from 3.5 to 6.5. The optimization of fermentation medium was carried out in shaking flasks. Recombinant protein expression at optimum conditions (pH 7, temperature 25 °C, and 1 % methanol induction) for 72 h demonstrated 2,358.8 U/ml endoglucanase activity units. To our knowledge, this is the highest acidic thermophilic endoglucanase activity that is reported in crude intracellular medium in P. pastoris. We conclude that P. pastoris is an appropriate host for high-level expression of optimized endoglucanase gene with improved thermal stability.     

Sorbent extraction behavior of a nonionic surfactant,Triton X-100, onto commercial charcoal from low level radioactive waste

In nuclear power plants and nuclear laboratories, laundry wastewater is generated from decontaminating polluted instruments, worker’s clothes and taking shower after work. Laundry wastewater contains radionuclides and surfactants. The surfactants included in laundry wastewater affect the extraction of radionuclides. Therefore, surfactants should be removed before extraction of radionuclides. The objective of the present work is to assess the ability of commercial charcoal for the removal of nonionic surfactants, where, commercial charcoal is a commonly available adsorbent for treatment. Charcoal was characterized using different analytical techniques. The isotherm models and thermodynamic parameters were evaluated. Charcoal was applied to the removal of surfactant from liquid radioactive waste. The data obtained can be used for designing a plant for treatment of surfactant rich water and wastewater economically.