Effects of polymer micelles of alkylated polyethylenimines on generation of gold nanoparticles

Mono- and di-alkylated polyethylenimines (PEI-1R, PEI-2R) were synthesized and used as both reductants, by exploiting the functionality of the polyethylenimine's (PEI) amino groups, and stabilizers able to protect nascent gold nanoparticles generated from hydrogen tetrachloroaurate (HAuCl4). From TEM images of the stained polymers, it is clear that the polymer micelles are round and well-structured when formed from PEI-2R, fused and less well-structured when formed from PEI-1R, and totally nonstructured when formed from PEI. These findings coincide with the results found by using pyrene as a probe to investigate aggregation behavior, where PEI-2R with a fluorescence intensity ratio (I1/I3) of 1.48 forms the more closely packed polymer micelles than PEI-1R (I1/I3 = 1.64) and PEI (I1/I3 = 1.72). The use of the highly alkylated polymer micelle (PEI-2R) results in the fastest reduction of HAuCl4, and gives the most effective protection to the generated gold nanoparticles. When used at higher polymer concentrations than required for micelle formation, it was found that polymer hydrophobicity was highly influential in directing the nanoparticle's morphology, i.e., the resulting polymer micelles were labeled with perfect and round necklace-like gold nanoparticles when PEI-2R was used, and imperfect and less round gold nanoparticles when PEI-1R was employed. These structures were totally absent when PEI was used. The use of alkylated PEI, being able to act simultaneously as both a reductant and as a very effective protective agent, greatly simplifies the process used for preparing gold nanoparticles.     

Vibrational band contours: III. Some observations on data processing of liquid-phase band contours

Procedures for correcting band shapes for distortions arising from a variety of factors are reviewed. A correction formula for instrument distortion is derived for the case where the instrument function may be represented by a Gaussian. It is demonstrated that it differs little from the analogous triangular slit function correction. Problems associated with the Fourier transformation of bands consisting of several overlapping components, and with interrelating first- and second-order rotational orientation functions are discussed.     

Benzoannulation of Quinones by a Cycloaddition‐Fragmentation Approach. A Simple Synthesis of Methoxycarbonyl‐Substituted Polyacenoquinones

The cycloadducts 2A‐5A obtained from the Diels‐Alder cycloadditions of 1,2,3,4‐tetrachloro‐4,5‐dimethoxycyclopentadiene ( 1 ) with p‐benzoquinone ( 2 ), 1,4‐naphthoquinone ( 3 ), 1,4‐anthraquinone ( 4 ), and 2,3‐dicyano‐1,4‐benzoquinone ( 5 ) were subjected to the reaction with triethylamine in dichloromethane at room temperature. Cycloadducts 2A and 5A enolized to give the corresponding hydroquinones 2B and 5B , which were oxidized with DDQ to afford naphthoquinone ester 2D and anthraquinone ester 5D , respectively. In the cases of cycloadducts 3A and 4A , the enolization occurred concurrently with oxidation and fragmentation to produce directly the polyacenoquinone esters 3D and 4D , respectively. Under the same reaction condition, the unsymmetrical cycloadduct 6A derived from naphthoquinone ester 2D and 1 yielded isomeric polyacenoquinone esters 6Da and 6Db in a ratio of about 8:1.     

Characterization of gelatin nanofibers electrospun using ethanol/formic acid/water as a solvent

Gelatin nanofibers were prepared via electrospinning using aqueous solutions of formic acid and ethanol as the solvent instead of cytotoxic solvents. The resulting mat was further crosslinked with glutaraldehyde (GTA). The influence of the storing time on the viscosity and gel point of the solution was investigated. The gelatin nanofibers were examined using a field emission scanning electron microscope (FESEM) for the fiber size and morphology. The lowest diameter of gelatin fiber (85 nm, without beads) was achieved when the gelatin concentration was 20 wt% and electrospinning was conducted with a voltage of 20 kV over a distance of 10 cm at ambient temperature. The results from differential scanning calorimetry (DSC) showed that the softening temperature of gelatin nanofibers crosslinked with GTA was elevated. In addition, GTA‐crosslinked gelatin nanofibers exhibited cell compatibility for mouse mesangial cells (CRL 1927). Copyright © 2008 John Wiley & Sons, Ltd.     

Standing wave enhancement of red absorbance and photocurrent in dye-sensitized titanium dioxide photoelectrodes coupled to photonic crystals

The light harvesting efficiency of dye-sensitized photoelectrodes was enhanced by coupling a TiO(2) photonic crystal layer to a conventional film of TiO(2) nanoparticles. In addition to acting as a dielectric mirror, the inverse opal photonic crystal caused a significant change in dye absorbance which depended on the position of the stop band. Absorbance was suppressed at wavelengths shorter than the stop band maximum and was enhanced at longer wavelengths. This effect arises from the slow group velocity of light in the vicinity of the stop band, and the consequent localization of light intensity in the voids (to the blue) or in the dye-sensitized TiO(2) (to the red) portions of the photonic crystal. By coupling a photonic crystal to a film of TiO(2) nanoparticles, the short circuit photocurrent efficiency across the visible spectrum (400-750 nm) could be increased by about 26%, relative to an ordinary dye-sensitized nanocrystalline TiO(2) photoelectrode.     

Studies on certain physical properties of modified smectite nanocatalysts

Most volatile organic compounds (VOCs) are toxic to humans in some manner. Generally, transitional metal catalysts have better conversion rates for controlling VOCs. However, catalyst activity will decay at high temperature, though the oxidizing catalyst is cheap. This study used smectite as the carrier to exchange with Ag⁺, Zn²⁺ and Ti⁴⁺ to modify the surface and form smectite catalysts. In addition, the transmission electron microscopy (TEM), FT-IR spectrum, and DSC-TGA instrument were applied to characterize their physical properties. After the FT-IR analysis of the modified smectite catalyst (smectite-Ag, smectite-Zn and smectite-Ti), both smectite and smectite catalyst had significant and complicated wave crests between the fingerprint area with the wave numbers of 415-600 cm⁻¹ and 750-1170 cm⁻¹, that indicated the existence of a strong bond between impure silicates (Si-O) and silicates (O-Si-O). TEM observation proved that sintering at 350 °C results in the distribution of catalyst ions on clay carrier with a nanoscale. As thermal analysis reveals, the smectite reached endothermic peaks at the temperatures of 920 °C and 1057 °C, respectively, and shows the decomposition in a non-crystal form. Besides, the disappearance of the endothermic peak of smectite-Ag occurs at 920.5 °C and the exothermic peak occurs at 950 °C. The results indicating crystals formed of smectite-Ag are more comprehensive and stable than the other smectite or modified smectite catalysts at high temperature.