Stability shear stress and equilibrium cross-sectional geometry of sheltered tidal channels

This study relates tidal channel cross-sectional area (A) to peak spring discharge (Q) via a physical mechanism, namely the stability shear stress ( tau sub(S)) just necessary to maintain a zero gradient in net along-channel sediment transport. It is assumed that if bed shear stress ( tau ) is greater than tau sub(S), net erosion will occur, increasing A, and reducing tau similar to (Q/A) super(2) back toward tau sub(S). If tau < tau sub(S) there will be net deposition, reducing A and increasing tau toward tau sub(S). A survey of the literature allows estimates of Q and A at 242 sections in 26 separate sheltered tidal systems. Assuming a single value of tau sub(S) characterizes the entire length of a given tidal channel, it is predicted that along-channel geometry will follow the relation Ah sub(R) super(1) super(/) super(6) similar to Q. Along-channel regressions of the form Ah sub(R) super(1) super(/) super(6) similar to Q super( beta ) give a mean observed value for beta of 1.00 plus or minus 0.06, which is consistent with this concept. Results indicate that a lower bound on tau sub(S) (and an upper bound on A) for stable channels is provided by the critical shear stress ( tau sub(C)) just capable of initiating sediment motion. Observed tau sub(S) is found to vary among all systems as a function of spring tidal range (R sub(sp)) according to the relation tau sub(S) approximately 2.3 R sub(sp) super(0.79) tau sub(C). Observed deviations from uniform tau sub(S) along individual channels are associated with along-channel variation in the direction of maximum discharge (i.e., flood-versus ebb-dominance).

Styrene polymerization catalyzed by metal porphyrin complex/MAO for in situ synthesizing polystyrene containing air stable pi cation radicals

A novel catalyst system based on nickel(II) tetraphenylporphyrin (Ni(II)TPP) and methylaluminoxane for styrene polymerization was developed. This catalyst system has a high thermal stability and show fairly good activity. The obtained polystyrene (PS) was isotactic-rich atactic polymer by C-13 NMR analysis, and its molecular weight distribution was rather narrow (M-w/M-n approximate to 1.6, by GPC analysis). ESR revealed that Ni(II)TPP pi cation radicals were formed in the polymerization and could remain in the resulting PS stably. The mechanism of the polymerization was discussed and a special coordination mechanism was proposed. The PS product containing Ni(II)TPP pi cation radicals can be used as a potential functional material.

Metallic Cation Induced One-Dimensional Assembly of Poly(acrylic acid)-1-Dodecanethiol-Stabilized Gold Nanoparticles

In this work, we report a simple approach for controllable synthesis of one-dimensional (ID) gold nanoparticle (AuNP) assemblies in solution. In the presence of divalent metallic ions, poly(acrylic acid)-1-dodecanethiol-stabilized AuNPs (PAA-DDT@AuNPs) are found to form I D assemblies in aqueous solution by an ion-templated chelation process; this causes an easily measurable change in the absorption spectrum of the particles. The assemblies are very stable and remain suspended in solution for more than one month without significant aggregation.

A ternary supramolecular compound of p-sulfonatocalix[8]arene with 1D channels

A ternary supramolecular complex of [Ni(bipy)(2)(H2O)](4)(C8AS)center dot 17.6(H2O) (bipy=4,4'-dimethyl-2,2'-bipyridine and C8AS = p-sulfonatocalix[8]arene) has been synthesized by a hydrothermal method and characterized by FT-IR spectroscopy, TG-DTA analysis and single crystal X-ray diffraction. In the structure. the water-soluble p-sulfonatocalix[8]arene molecule adopts a double partial cone conformation and is coordinated by four nickel atoms each of which is bonded by two 4,4'-dimethyl-2,2'-bipyridine molecules and one water molecule at the same time. The tetranuclear Subunits are stacked into an extended 3D structure with 1D water-filled channels via hydrogen bonds and C-H center dot center dot center dot pi interactions.

Harvesting Excitons Via Two Parallel Channels for Efficient White Organic LEDs with Nearly 100% Internal Quantum Efficiency: Fabrication and Emission-Mechanism Analysis

By incorporating two phosphorescent dyes, namely, iridium(III)[bis(4,6-difluorophenyl)-pyridinato-N,C-2']picolinate (Flrpic) for blue emission and bis(2-(9,9-diethyl-9H-fluoren-2-yl)-1-phenyl-1 H-benzoimidazol-N,C-3) iridium(acetylacetonate) ((fbi)(2)Ir(acac)) for orange emission, into a single-energy well-like emissive layer, an extremely high-efficiency white organic light-emitting diode (WOLED) with excellent color stability is demonstrated. This device can achieve a peak forward-viewing power efficiency of 42.5 lm W-1, corresponding to an external quantum efficiency (EQE) of 19.3% and a current efficiency of 52.8 cd A(-1). Systematic studies of the dopants, host and dopant-doped host films in terms of photophysical properties (including absorption, photoluminescence, and excitation spectra), transient photoluminescence, current density-voltage characteristics, and temperature-dependent electroluminescence spectra are subsequently performed, from which it is concluded that the emission natures of Flrpic and (fbi)(2)Ir(acac) are, respectively, host-guest energy transfer and a direct exciton formation process. These two parallel pathways serve to channel the overall excitons to both dopants, greatly reducing unfavorable energy losses.

PH-Dependent syntheses and structures of two Copper(II)/Phenanthroline/p-Sulfonatocalix[4]arene supramolecular compounds with 1D water-filled channels

Two copper-organic framework supramolecular assemblies of p-sulfonatocalix[4]arene and 1,10-phenanthroline Cu-2[C12H8N2][C28H20S4O16][H2O](23.5) (1) and Cu-3[C12H8N2](3)[C28H19S4O16]Cl[H2O](17.6) (2) were obtained by pH-dependent synthesis at room temperature. Both structures show ID water-filled channels (rectangular shape in I and triangular in 2) with the solvent-accessible volume occupying 30.8% (1) and 24.2% (2) of the unit-cell volume, respectively. The calixarene molecules in both structures assume analogous cone shapes of C-2 nu symmetry instead of the conventional C-4 nu symmetry. Their connecting to different amounts of copper/phenanthroline cations leads to the formation of different structures.

Facilitated ion-transfer of sodium cation by (anthraquinone-1-yloxy) methane-15-crown-5 across the water/1,2-dichloroethane microinterface

The transfer of sodium cation facilitated by (anthraquinone-1-yloxy) methane-15-crown-5(L) has been investigated at the water/1,2-dichloroethane microinterface supported at the tip of a micropipette. The diffusion coefficient of (anthraquinone-1-yloxy) methane-15-crown-5 obtained was (3.42 +/- 0.20) x 10(-6) cm(2) s(-1). The steady-state voltammograms were observed for forward and backward scans due to sodium ion transfer facilitated by L with 1:1 stoichiometry. The mechanism corresponded to an interfacial complexation (TIC) and interfacial dissociation (TID) process. The association constant was calculated to be log beta(o) = 11.08 +/- 0.03 in the DCE phase. The association constant of other alkali metals (Li+, K+, Rb+) were also obtained.

An ionic liquid based on a cyclic guanidinium cation is an efficient medium for the selective oxidation of benzyl alcohols

A novel room temperature ionic liquid (RTIL) has been prepared containing a cyclic hexaalkylguanidinium cation. The selective oxidation of a series of substituted benzyl alcohols has been carried out in it, with sodium hypochlorite as the oxidant. The RTIL acts as both phase transfer catalyst (PTC) and solvent. The ionic liquid could be recycled after extraction of the benzaldehyde product with ether.

Ionic liquid solvent based on cyclic guanidinium cation for nucleophilic displacement reactions

The nucleophilic displacement reaction of n-bromooctane and potassium iodide in ionic liquid based on cyclic guanidinium cation(2) was investigated. The kinetic reasult shows that the rate of the reaction is enhanced in ionic liquid (2). The same reaction in [bmim][PF6](1)(where bmim = 1-butyl-3-methylimidazolium) was also studied. It was found that as a reaction medium ionic liquid (2) is better than (1) for nucelophilic displacement reactions.

Anion coordination and molecular assembly in C2-substituted thiamine-anion systems: effects of the anion and molecular conformation

The compounds (het)(PtCl6)2H(2)O 1, (het)(HgI4).H2O 2 (het = 2-(alpha-hydroxyethyl)thiamine) and (hpt)(Hg2Br6) 3 (hpt = 2-(alpha-hydroxypropyl)thiamine) have been prepared and structurally characterized by X-ray crystallography in order to study the influence of the anion and molecular conformation on the formation of supramolecular architectures that adsorb anionic species. Both het and hpt molecules adopt the usual S conformation for C2-substituted thiamine but differ from the F conformation for C2-free thiamine derivatives. Two types of characteristic ligand-anion complexation are observed, being of the forms C(6')-H...anion...thiazolium-ring (in 1 and 2) and N(4'1)-H...anion...thiazolium-ring (in 3). The reaction of het with PtCl62- or HgI42- gives a 1-D double-chain in 1, consisting of two hydrogen-bonded het chains, which are cross-linked by anions through hydrogen bonding and anion...aromatic-ring interactions, or a cationic 3-D framework in 2 formed by the stacking of hydrogen-bonded sheets with anion-and-water-filled channels. In the case of 3, hydrogen-bonded hpt dimers and HgBr62- anions form alternate cation-anion columns. A comparison with the cases of C2-free thiamine-anion complexes indicates that the change in molecular conformation results in novel supramolecular assemblies in 1 and 2 and an analogous architecture in 3, which also depends on the nature of the anions.

New high-dimensional networks based on polyoxometalate and crown ether building blocks

Three novel supramolecular assemblies constructed from polyoxometalate and crown ether building blocks, [(DB18C6)Na(H2O)(1.5)](2)Mo6O19.CH3CN, 1, and [{Na(DB18C6)(H2O)(2)}(3)(H2O)(2)]XMo12O40.6DMF.CH3CN (X = P, 2, and As, 3; DB18C6 = dibenzo-18-crown-6; DMF = N,N-dimethylfomamide), have been synthesized and characterized by elemental analyses, IR, UV-vis, EPR, TG, and single crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group P4/mbm with a = 16.9701(6) Angstrom, c = 14.2676(4) Angstrom, and Z = 2. Compound 2 crystallizes in the hexagonal space group P6(3)/m with a = 15,7435(17) Angstrom, c = 30.042(7) Angstrom, gamma = 120degrees, and Z = 2. Compound 3 crystallizes in the hexagonal space group P6(3)/m with a = 15.6882(5) Angstrom, c = 29.9778(18) Angstrom, gamma = 120degrees, and Z = 2. Compound 1 exhibits an unusual three-dimensional network with one-dimensional sandglasslike channels based on the extensive weak forces between the oxygen atoms on the [Mo6O19](2-) polyoxoanions and the CH2 groups of crown ether molecules, Compounds 2 and 3 are isostructural, and both contain a novel semiopen cagelike trimeric cation [{Na(DB18C6)(H2O)(2)}(3)(H2O)(2)](3+). In their packing arrangement, an interesting 2-D "honeycomblike" "host" network is formed, in which the [XMo12O40](3-) (X = As and P) polyoxoanion "guests" resided.

Synthesis and structure of a novel open-framework zincophosphate with intersecting three-dimensional helical channels

A new open-framework zincophosphate, Zn-0.5(H2PO4).0.5H(2)O (denoted as FJ-13), possessing intersecting three-dimensional helical channels, has been synthesized under solvothermal conditions.

Cation selectivity of perfluorosulfonate polymer

Selectivity coefficient measurement has been performed for K+,Ni2+,Fe3+ with Nafion 117 perfluorosulfonate polymer as-received forms. The results show that a linear Nernst response is exhibited for H+,K+,Pb2+,Ni2+,Co2+,Fe3+, and the ion selectivity coefficient of Nafion membrane for KC is better than Ni2+ and Fe3+.

Influence of cation concentration on 7,7,8,8-tetracyanoquinodimethane in polyelectrolyte by using in-situ microscopic Fourier transform infrared spectroelectrochemistry

The ion pair between the dianion of 7,7,8, 8-tetracyanoquinodimethane(TCNQ) and Li+ were investigated by in - situ microscopic Fourier transform infrared( FTIR) spectroelectrochemical technique. The effect of ion pair increases with increasing the concentration of cation. We observed a new band at 2130 cm(-1).

Electrochemical study of gramicidin D forming ion-permeable channels in the bilayer lipid membranes

Gramicidin within the lipid bilayer matrix is a well-known channel-forming polypeptide, but the mechanism of the ions across the membrane induced by gramicidin is not well understood. We found that at very low concentration of gramicidin in a bilayer lipid membrane, the channel behavior was controlled by the voltage applied across the membrane. When the voltage is higher than 75 mV, the channel is closing, while lower than 75 mV, the channel is opening. But when the concentration of the gramicidin in the BLMs is high, the channel behavior is changed into voltage-independent. (C) 1998 Elsevier Science Ltd. All rights reserved.