Concentrated reverse micelles in a random graft block copolymer system: structure and in-situ synthesis of silver nanoparticles

The structure and rheological properties of a poly(dimethylsiloxane)-graft-poly(oxyethylene) copolymer at high concentrations in block-selective solvents were studied by small-angle X-ray scattering (SAXS) and rheometry. Analysis of SAXS data indicates that quasispherical, reverse micellar aggregates (with no ordered packing) are present in concentrated solutions of the copolymer in nonpolar solvents, and that upon addition of water, the size of such aggregates increases due to the solubilization inside the micellar cores. The viscosity of concentrated polymer solutions increases exponentially as water is added, and finally, viscoelastic, gel-like behavior is found in the vicinity of the phase separation limit. It was found that small silver nanoparticles with an average diameter of ≈3 nm can be synthesized inside the copolymer aggregates without the need of a reducing agent; namely, particles embedded in a viscoelastic matrix are obtained. The synthesis seems to follow first-order kinetics. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Ion-pair adsorption film colorimetry — A new simple method for ppb level of aluminum ion in water sample

A new, highly sensitive and simple colorimetric method for trace aluminum(III) with 2,2-dihydroxyazobenzene, H₂L, is described, based on the ion-pair adsorption of the anionic Al chelate, [A1L₂ ^–, with crystal violet cation, CV⁺, on the surface of Polyvinylchloride film plasticized with dioctylphthalate. The blue violet species, CV⁺[A1L₂]^–, is enriched onto the transparent film, leading to a remarkable enhancement of the sensitivity, and the detection limits are 3 ng/ml by spectrophotometry and 5 ng/ml by visual colorimetry, respectively. Using spectrophotometer, a linear calibration curve is obtained over the concentration range of 0 to 50 ng/ml of Al. Further, the color system, consisting of red ([A1L₂]^–), yellow (H₂L), and blue violet (CV⁺), gave clear color changes suitable for visual determination of aluminum with an applicable range of 0 to above 3000 ng/ml. The four different color zones are khaki for 0–5 ng/ml, reddish-brown for 5–200 ng/ml, blue violet for 200 ng/ml-3g/ml, and colorless for more than 3g/ml. The proposed method has been successfully applied for the determination of aluminum in tap waters.     

A mixed version of Menger's theorem

An(a, b)-n-fan means a union ofn internally disjoint paths. Menger's theorem states that a graphG has an(a, b)-n-fan if and only ifG isn-connected betweena andb. We show thatG contains edge-disjoint(a, b)-n-fans if and only if for anyk withk0min{n–1, |V(G)|–2} and for any subsetX ofV(G)-{a, b} with cardinalityk, G-X is (n-k)-edge-connected betweena andb.     

Evolution of host-parasitoid network through homeochaotic dynamics

Host-parasitoid systems with evolving mutation rates are studied. By increasing the growth rate of hosts, the diversity of both species is maintained dynamically. For the lower growth rate, diversity is brought about by mere parasitism. The average mutation rate for parasites is elevated to a high value, while that for hosts is suppressed at a low level. For the higher growth rate, the mutation rates for both hosts and parasites are elevated to form a symbiotic cluster connected by on-going mutation. This symbiotic state is sustained through a chaotic oscillation keeping some coherency among species. For a flat landscape for hosts, dynamical clustering of oscillation is observed. Lyapunov spectra of such oscillations show that high dimensional chaos with small positive exponents underlies in the symbiotic state. This weak high dimensional chaos, termed "homeochaos," is essential to the maintenance of symbiosis in ecosystems.     

ESR Study of a Nitroxide Radical in Sol-Gel Glasses

A spin probe TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxy) was dissolved in a tetraethyl orthosilicate sol-gel reaction system and measured by electron spin resonance spectroscopy at 295 K. The nitrogen hyperfine coupling constant was from 1.64–1.66 mT in the sol-gel solutions. The values were sensitive to the ethanol-to-water ratio of the solutions. The hyperfine coupling constant in the xerogels was 1.70 mT, which was almost the same as that in water, indicating that the probe molecules were trapped in silica pores with water adsorbed on the silica surfaces. The motion of TEMPOL in the xerogels was considerably slower than in the sol-gel solutions. The local viscosity estimated was from 70–90 cP. The ESR spectra of TEMPOL were altered during the sol-gel process, indicating that adsorbed water on the silicas surfaces has an important role for trapping organic molecules in sol-gel glasses.     

Water cluster growth in hydrophobic solid nanospaces

The growth mechanism of water clusters in carbon nanopores is clearly elucidated by in situ small-angle X-ray scattering (SAXS) studies and grand canonical Monte Carlo (GCMC) simulations at 293-313 K. Water molecules are isolated from each other in hydrophobic nanopores below relative pressures (P/P(0)) of 0.5. Water molecules associate with each other to form clusters of about 0.6 nm in size at P/P(0)=0.6, accompanied by a remarkable aggregation of these clusters. The complete filling of carbon nanopores finishes at about P/P(0)=0.8. The correlation length analysis of SAXS profiles leads to the proposal of a growth mechanism for these water clusters and the presence of the critical cluster size of 0.6 nm leads to extremely stable clusters of water molecules in hydrophobic nanopores. Once a cluster of the critical size is formed in hydrophobic nanopores, the predominant water adsorption begins to fill carbon nanopores.     

Chemical synthesis of the 5-́half molecule of E.coli tRNA2GLY

A tritriacontanucleotide which has the sequence of the 5$\text{-}\text{?}$half molecule of E.coli glycine tRNA₂, was synthesized by the phosphotriester method involving p-anisidate protection for the 3$\text{-}\text{?}$phosphate ends. Di- and trinucleotide units were prepared from 5$\text{-}\text{?}$dimethoxytrityl-2$\text{-}\text{?}$O-tetrahydrofuranyl-3?-O-(o-chlorophenyl)phosphoryl derivatives of uridine, N-benzoylcytidine, N-benzolyadenosine and N-iso-butyrylguanosine by condensation with 3$\text{,}\text{?}$5$\text{-}\text{?}$unprotected nucleosides followed by phosphorylation to give 3$\text{-}\text{?}$phosphodiester blocks. The 3$\text{-}\text{?}$terminal dimers and trimers were synthesized by using 3$\text{-}\text{?}$(o- chlorophenyl)phosphoro-p-anisidates instead of 3?,5?-unprotected nucleosides. The 3?-phosphodiesters of oligonucleotides with a chain length of larger than 5 were obtained by removal of the 3?-phosphoro-p-anisidate with isoamyl nitrite. The 5$\text{-}\text{?}$dimethoxytrityl group was removed by treatment with zinc bromide under anhydrous conditions. Fragments were designed to use common dimer blocks and to reduce the step for 5$\text{-}\text{?}$deblocking of larger fragments. Finally a 3$\text{-}\text{?}$phosphodiester block with a chain length of 20 was condensed with a 5$\text{-}\text{?}$OH component (tridecanucleotide). The fully protected 33 mer was deblocked and purified by chromatography. The structural integrity of the product was confirmed by mobility shift analysis and complete digestion with RNase T2.     

Photosensing Device Composed of Bilayer Membranes of Polymer-Pendant Ru(bpy)3 2+ and Prussian Blue

A photosensing device was fabricated based on a photochemical electron transfer reaction. A graphite electrode was coated with bilayer membranes of polymer-pendant Ru(bpy)₃ ²⁺ and Prussian Blue (PB) to give a bilayer-coated device. It was irradiated with visible light in an aqueous electrolyte and the induced photocurrent was measured as a function of the applied potential. The excitation of PB was responsible for the anodic photocurrent, while the excitation of the Ru complex mainly induced the cathodic photocurrent by an electron-transfer mechanism.