Nanostructure of silver metal produced photocatalytically in TiO2 films and the mechanism of the resulting photochromic behavior

The optical activity of composite films created by the photocatalytic reduction of silver or gold ions in TiO(2) upon irradiation by UV light has up to now been discussed in terms of the formation and light-induced destruction of distinct nanoparticles molded inside the porous nanocrystalline film. We present results from classical light scattering calculations and a logical analysis of experimental observations to add detail to the mechanism. As opposed to large, solid metal nanoparticles, coatings and small particles in heterogeneous external dielectric environments account for observations such as the broad optical spectrum and multiwavelength photochromic responses. For some steps of the photochromic process, we propose that visible light permits an equilibrium promoting the growth of small metal features or suspended particles. We use a new expression for the restricted path length in our size-dependent broadening corrections of metal shells and discuss this briefly. We conclude by discussing the consequence of plasmon absorption in the proximity of the electronically active TiO(2) surrounding matrix, leading to mass transfer and shape change of the metal and photochromic properties of the film.     

Investigation of a Unified Chaotic System and Its Synchronization by Simulations*

We investigate a unified chaotic system and its synchronization including feedback synchronization and adaptive synchronization by numerical simulations. We propose a new dynamical quantity denoted by K, which connects adaptive synchronization and feedback synchronization, to analyze synchronization schemes. We find that K can estimate the smallest coupling strength for a unified chaotic system whether it is complete feedback or one-sided feedback. Based on the previous work, we also give a new dynamical method to compute the leading Lyapunov exponent.     

Dendritic Macromolecules as Inhibitors to Protein-Protein Binding

Summary: Our initial studies into protein binding using a series of dendrimers as size selective inhibitors have been described. Two different proteins, cytochromo-c and chymotrypsin have been selected for these binding experiments.     

On the Spectra of Left-Definite Operators

If A is a self-adjoint operator that is bounded below in a Hilbert space H, Littlejohn and Wellman (J Diff Equ 181(2):280–339, 2002) showed that, for each r > 0, there exists a unique Hilbert space H _r and a unique self-adjoint operator A _r in H _r satisfying certain conditions dependent on H and A. The space H _r and the operator A _r are called, respectively, the rth left-definite space and rth left-definite operator associated with (H, A). In this paper, we show that the operators A, A _r , and A _s (r, s > 0) are isometrically isomorphically equivalent and that the spaces H, H _r , and H _s (r, s > 0) are isometrically isomorphic. These results are then used to reproduce the left-definite spaces and left-definite operators. Furthermore, we will see that our new results imply that the spectra of A and A _r are equal, giving us another proof of this phenomenon that was first established in Littlejohn and Wellman (J Diff Equ 181(2):280–339, 2002).     

Formulae for null curves deriving from elliptic curves

Any elliptic curve can be realised in the tangent bundle of the complex projective line as a double cover branched at four distinct points on the zero section. Such a curve generates, via classical osculation duality, a null curve in C³${\mathbb{C}}^3$ and thus an algebraic minimal surface in R³${\mathbb{R}}^3$. We derive simple formulae for the coordinate functions of such a null curve.     

Directed-Backbone Dissociation Following Bond-Specific Carbon-Sulfur UVPD at 213 nm

Ultraviolet photodissociation or UVPD is an increasingly popular option for tandem-mass spectrometry experiments. UVPD can be carried out at many wavelengths, and it is important to understand how the results will be impacted by this choice. Here, we explore the utility of 213 nm photons for initiating bond-selective fragmentation. It is found that bonds previously determined to be labile at 266 nm, including carbon-iodine and sulfur-sulfur bonds, can also be cleaved with high selectivity at 213 nm. In addition, many carbon-sulfur bonds that are not subject to direct dissociation at 266 nm can be selectively fragmented at 213 nm. This capability can be used to site-specifically create alaninyl radicals that direct backbone dissociation at the radical site, creating diagnostic d-ions. Furthermore, the additional carbon-sulfur bond fragmentation capability leads to signature triplets for fragmentation of disulfide bonds. Absorption of amide bonds can enhance dissociation of nearby labile carbon-sulfur bonds and can be used for stochastic backbone fragmentation typical of UVPD experiments at shorter wavelengths. Several potential applications of the bond-selective fragmentation chemistry observed at 213 nm are discussed.

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Nil subsets of graded algebras

We prove that if is a Noetherian -graded algebra, then the Jacobson radical of is nilpotent under mild hypotheses on . We also consider affine PI-algebras graded by torsion groups. Finally we prove a Nullstellensatz-type theorem for enveloping algebras of Lie color algebras.

     

Methylene blue derivatization then LC–MS analysis for measurement of trace levels of sulfide in aquatic samples

The methylene blue method has been widely used for analysis of sulfide for more than 100 years. Direct measurement of methylene blue at nanomolar concentrations is impossible without a preconcentration step, however. In this study the response of LC–MS with electrospray ionization (ESI) to methylene blue was evaluated. HPLC with simple isocratic elution was followed by ESI-MS quantification, which was compared with traditional UV–visible detection. The limit of detection for sulfide was approximately 50 ng L⁻¹, or 1.5 nmol L⁻¹. Analysis time was substantially reduced by use of isocratic elution. Interfering compounds produced by side reactions can be eliminated by use of the mass filter. A polysulfide sample was also analyzed to determine which products are formed and whether or not polysulfides react stoichiometrically with methylene blue reagent. It seems that polysulfides do not react quantitatively with methylene blue and so cannot be quantified reliably by use of this method.     

Synthesis and characterization of immobilized PAMAM dendrons

This communication describes the synthesis and characterization of immobilized PAMAM dendrons onto a surface modified silicon wafer substrate (functionalized using plasma polymerized PAA) using a "growing from" strategy.